Integrated process for treating recycled streams of pet and ptt

ABSTRACT

A process for producing a polyester polyol comprising reacting a recycle stream selected from recycled PET carpet, carpet fiber, containers, textiles, articles or mixtures thereof, with a glycol in a reactor, thereby forming a digested product stream comprising polyols, and an undigested stream; and then reacting the digested product stream with a hydrophobe selected from dimer fatty acids, trimer fatty acids, oleic acid, ricinoleic acid, tung oil, corn oil, canola oil, soybean oil, sunflower oil, bacterial oil, yeast oil, algae oil, castor oil, triglycerides or alkyl carboxylate esters having saturated or unsaturated C 6 -C 36  fatty acid units, saturated or unsaturated C 6 -C 36  fatty acids, alkoxylated castor oil, saturated or unsaturated C 9 -C 18  dicarboxylic acids or diols, cardanol-based products, recycled cooking oil, branched or linear C 6 -C 36  fatty alcohols, hydroxy-functional materials derived from epoxidized, ozonized, or hydroformylated fatty esters or acids, or mixtures thereof.

FIELD OF THE INVENTION

The invention relates to a process for producing polyester polyols andplasticizers from recycle PET & PTT streams. More particularly, theinvention relates to an integrated process for producing polyesterpolyols by digestion of recycled PET or PTT carpet, carpet fiber, yarn;PET containers, textiles, string, twine or other recycled PET or PTTarticles with glycol, and reaction of the digested material with ahydrophobe.

BACKGROUND OF THE INVENTION

The use of thermoplastic, polyester-based consumer products such aspolyethylene terephthalate (PET) have become so widespread over the lastfew decades that they have become a fixture of modern day life. PET isused in carpet fibers, and primary and secondary carpet backings such asbacking cushions. PET bottles have come to package virtually all commonnon-alcoholic drinks, spanning the range from water bottles tocarbonated beverages to sports drinks. However, as a result of theirpopularity and the length of time required for the natural breakdown ofthe PET plastics, efforts have long been made to recycle the PETcontaining materials. Such recycling efforts have continued to be animportant consumer consideration for several reasons. First, virgin PETis produced from petrochemicals, so that reducing the use of new bottleswould lower oil consumption. Second, the recycling and reuse of recycledPET lowers emission of greenhouse gases as compared to the emissionsthat are generated from the extraction of oil, conversion of oil intoPET intermediates, and the manufacture of final virgin PET product.Finally, recycling PET bottles or carpet and any of its components saveslandfill space. Many landfills are closing, and permits for newlandfills are very difficult, if not impossible, to obtain. Moreover,many high density population cities such as Seattle or New York, do nothave landfill space, and consequently ship their daily waste via rail orbarge, hundreds of miles to other states where landfill space isavailable. This space issue is a high-profile concern to modernconsumers, states and municipalities, who have increasingly embraced thedesirability of sustainable technologies. Indeed, such a sentiment hasbeen demonstrated in related applications, where states such asCalifornia or cities such as New York have banned the use of plasticgrocery bags or polystyrene cups. Recycling systems using a variety ofmechanical or chemical processes for nylon and polypropylene-basedcarpet are known. However, over 95% of all PET carpeting is deposited inlandfills. New and more flexible methods of recycling PET carpetcomponents are needed to relieve the hundreds of millions of pounds ofPET carpeting going into landfills today. There is thus a growing needfor efficient processes to recycle PET carpet.

Current recycle methods for PET bottles typically involve the separationof colored and non-colored bottles from other recyclables andcontaminants in the recycle stream. Caps, labels, adhesives and capseals contained in the PET bottles are also removed prior to digestionin glycol, since they are made of polyolefins, not PET. Unfortunately,the purification of PET is a relatively complicated process. Onemanufacturer's process involves: (i) processing the bottles in a drytrommel machine to eliminate contaminants such as dirt or otherparticulates; (ii) treating the bottles with a magnetic field toeliminate ferromagnetic materials; (iii) washing to separate labels andadhesives from the bottles; (iv) processing the bottles through a secondtrommel machine to separate the PET from the labels and some of thelids; (v) auto-sorting the bottles using near-infrared detectorscombined with pneumatic air streams to separate colored bottles fromnon-colored bottles; (vi) sorting the bottles manually to correct errorsmade by the near-infrared detection step; (vii) chopping the bottlesinto flakes; (viii) separating the polyolefin lids and seals from thehigher density PET by floatation separation in water; (ix) washing theresulting PET flakes to further remove contaminants on formerly interiorsurfaces, labels and adhesive residues; (x) dewatering and drying toremove water; (xi) processing the flakes through a separator thatremoves aluminum contaminants; and optionally as a final step, (xii)melt processing the resulting flakes at high temperature in an extruderwith filtering via a stainless steel screen pack to further reducecontaminants. It would be desirable to simplify this complicated processby reducing the number of steps involved, thereby making the entireprocess more cost effective, more environmentally friendly and moresustainable, since such streamlining would encourage even greaterrecycling rates throughout the world.

Following purification of the recycled PET material, a glycol digestionprocess may be used to convert the PET polymers to a mixture of glycolsand low-molecular-weight PET oligomers. However, although such mixtureshave desirably low viscosities (low molecular weight), they often havehigh hydroxyl numbers or high levels of free glycols.

Furthermore, digestion of recycled PET bottles without an initialseparation of the polyolefin material has been disclosed, e.g., as inJP-2000-198876, JP-2004-238581 and JP-2005-002161), however, suchmethods can result in softened polyolefin material that agglomerates orclogs processing machinery, complicating its removal from the digestedliquid.

Finally, although digested, recycled PET material can be reacted withvarious hydrophobic materials to increase its molecular weight, many ofthe conventional hydrophobes used yield solid, thick, or opaqueproducts; polyols that have substantial particulates; or polyols thatseparate into two phases. However, this is unacceptable for urethaneformulations, which require polyester polyols to meet specifications forcolor, clarity, hydroxyl number, functionality, acid number, viscosity,and other properties.

Therefore, improved processes for producing sustainable polyols fromrecycled PET for the urethane industry are needed that not only minimizeprocessing difficulties and improve sustainability but provide polyesterpolyols having the desired properties. It has unexpectedly been foundthat producing polyester polyols and plasticizers from a recycle streamof PTT or PET carpet, carpet fibers, yarn; PET containers, textiles,twine, string, or other PET or PTT recycled articles in an integratedrecycling process using particularly defined hydrophobes and modifiers,can provide the required specifications for polyurethane andpolyisocyanurate applications.

SUMMARY OF THE INVENTION

The invention relates to processes for producing polyester polyols andplasticizers by an integrated process, where a recycle stream of PTT orPET carpet, carpet fibers, yarn; PET containers, textiles, string, twineor other recycled PET articles is reacted with glycol and hydrophobes.

In one embodiment, the present disclosure provides a process comprisingfirst reacting a recycle stream selected from recycled PET carpet,recycled PET carpet fiber, recycled PET containers, recycled PETtextiles, other recycled PET articles or mixtures thereof, with a glycolin a reactor, thereby forming a digested product stream comprisingpolyols, and at least one undigested stream. Then, the digested productstream is reacted in the reactor with a hydrophobe selected from dimerfatty acids, trimer fatty acids, oleic acid, ricinoleic acid, tung oil,corn oil, canola oil, soybean oil, sunflower oil, bacterial oil, yeastoil, algae oil, castor oil, triglycerides or alkyl carboxylate estershaving saturated or unsaturated C₆-C₃₆ fatty acid units, saturated orunsaturated C₆-C₃₆ fatty acids, alkoxylated castor oil, saturated orunsaturated C₉-C₁₈ dicarboxylic acids or diols, cardanol-based products,recycled cooking oil, branched or linear C₆-C₃₆ fatty alcohols,hydroxy-functional materials derived from epoxidized, ozonized, orhydroformylated fatty esters or acids, or mixtures thereof, therebyforming a polyester polyol.

In an alternate embodiment, the present disclosure provides a processcomprising reacting: (i) a recycle stream selected from recycled PETcarpet, recycled PET containers, recycled PET textiles, other recycledPET articles or mixtures thereof, (ii) a glycol; and (iii) a hydrophobeselected from dimer fatty acids, trimer fatty acids, oleic acid,ricinoleic acid, tung oil, corn oil, canola oil, soybean oil, sunfloweroil, bacterial oil, yeast oil, algae oil, castor oil, triglycerides oralkyl carboxylate esters having saturated or unsaturated C₆-C₃₆ fattyacid units, saturated or unsaturated C₆-C₃₆ fatty acids, alkoxylatedcastor oil, saturated or unsaturated C₉-C₁₈ dicarboxylic acids or diols,cardanol-based products, recycled cooking oil, branched or linear C₆-C₃₆fatty alcohols, hydroxy-functional materials derived from epoxidized,ozonized, or hydroformylated fatty esters or acids, or mixtures thereof,thereby forming a polyester polyol.

In still another alternative embodiment, the present disclosure providesa process comprising first reacting a recycle stream selected fromrecycled PET carpet, recycled PET carpet fiber, recycled PET textiles,bales of PET containers or mixtures thereof, with a glycol in a reactor,thereby forming a digested product stream comprising polyols, and atleast one undigested stream. Then, the digested product stream in thereactor is reacted with a modifier selected from C₃-C₈ dicarboxylicacids, their mono or dialkyl esters, mono or dialkenyl esters, oranhydrides, thereby forming a polyester polyol.

In still another alternative embodiment, the present disclosure providesa process comprising reacting a recycle stream comprising bales of PETcontainers with a glycol in a reactor, thereby forming a digestedproduct stream comprising polyols, and at least one undigested stream.Then the digested product stream is reacted in the reactor with at leastone of a modifier selected from C₃-C₈ dicarboxylic acids, their mono ordialkyl esters, mono or dialkenyl esters, or anhydrides, and ahydrophobe selected from dimer fatty acids, trimer fatty acids, oleicacid, ricinoleic acid, tung oil, corn oil, canola oil, soybean oil,sunflower oil, bacterial oil, yeast oil, algae oil, castor oil,triglycerides or alkyl carboxylate esters having saturated orunsaturated C₆-C₃₆ fatty acid units, saturated or unsaturated C₆-C₃₆fatty acids, alkoxylated castor oil, saturated or unsaturated C₉-C₁₈dicarboxylic acids or diols, cardanol-based products, recycled cookingoil, branched or linear C₆-C₃₆ fatty alcohols, hydroxy-functionalmaterials derived from epoxidized, ozonized, or hydroformylated fattyesters or acids, or mixtures thereof, thereby forming a polyesterpolyol.

In an alternate embodiment, the present disclosure provides a processcomprising reacting: (i) a recycle stream selected from recycled PETcarpet, recycled PET textiles, or mixtures thereof; (ii) a glycol; and(iii) a modifier selected from C₃-C₈ dicarboxylic acids, their mono ordialkyl esters, mono or dialkenyl esters, or anhydrides, thereby forminga polyester polyol.

In another alternate embodiment, the present disclosure provides aprocess comprising first reacting a recycle stream selected fromrecycled PET carpet, recycled PET containers, recycled PET textiles,other recycled PET articles or mixtures thereof, with a glycol in areactor, thereby forming a digested product stream comprising polyols,and at least one undigested stream. Then, the digested product stream isreacted in the reactor with a hydrophobe selected from dimer fattyacids, trimer fatty acids, oleic acid, ricinoleic acid, tung oil, cornoil, canola oil, soybean oil, sunflower oil, bacterial oil, yeast oil,algae oil, castor oil, triglycerides or alkyl carboxylate esters havingsaturated or unsaturated C₆-C₃₆ fatty acid units, saturated orunsaturated C₆-C₃₆ fatty acids, alkoxylated castor oil, saturated orunsaturated C₉-C₁₈ dicarboxylic acids or diols, cardanol-based products,recycled cooking oil, branched or linear C₆-C₃₆ fatty alcohols,hydroxy-functional materials derived from epoxidized, ozonized, orhydroformylated fatty esters or acids, or mixtures thereof; and amodifier selected from C₃-C₈ dicarboxylic acids, their mono or dialkylesters, mono or dialkenyl esters, or anhydrides, thereby forming apolyester polyol.

In still another alternate embodiment, the present disclosure provides aprocess comprising reacting: (i) a recycle stream selected from recycledPET carpet, recycled PET containers, recycled PET textiles, recycled PETarticles, or mixtures thereof; (ii) a glycol; (iii) a hydrophobeselected from dimer fatty acids, trimer fatty acids, oleic acid,ricinoleic acid, tung oil, corn oil, canola oil, soybean oil, sunfloweroil, bacterial oil, yeast oil, algae oil, castor oil, triglycerides oralkyl carboxylate esters having saturated or unsaturated C₆-C₃₆ fattyacid units, saturated or unsaturated C₆-C₃₆ fatty acids, alkoxylatedcastor oil, saturated or unsaturated C₉-C₁₈ dicarboxylic acids or diols,cardanol-based products, recycled cooking oil, branched or linear C₆-C₃₆fatty alcohols, hydroxy-functional materials derived from epoxidized,ozonized, or hydroformylated fatty esters or acids, or mixtures thereof;and (iv) a modifier selected from C₃-C₈ dicarboxylic acids, their monoor dialkyl esters, mono or dialkenyl esters, or anhydrides, therebyforming a polyester polyol.

In an alternate embodiment, the present disclosure provides a processcomprising reacting a recycle stream selected from recycled PET carpet,recycled PET carpet fiber, recycled PET bottles, recycled PET textiles,other recycled PET articles, or mixtures thereof, with a glycol in areactor, thereby forming a digested intermediate comprising polyols andcontaminants selected from colorants, dyes, pigments, inorganic fillers,undigested polymers or mixtures thereof. Then the digested intermediatecan be reacted with a polyisocyanate to form a product stream selectedfrom polyurethane, polyisocyanurate or an isocyanate terminatedprepolymer. The digested intermediate can also be reacted with ahydrophobe selected from dimer fatty acids, trimer fatty acids, oleicacid, ricinoleic acid, tung oil, corn oil, canola oil, soybean oil,sunflower oil, bacterial oil, yeast oil, algae oil, castor oil,triglycerides or alkyl carboxylate esters having saturated orunsaturated C₆-C₃₆ fatty acid units, saturated or unsaturated C₆-C₃₆fatty acids, alkoxylated castor oil, saturated or unsaturated C₉-C₁₈dicarboxylic acids or diols, cardanol-based products, recycled cookingoil, branched or linear C₆-C₃₆ fatty alcohols, hydroxy-functionalmaterials derived from epoxidized, ozonized, or hydroformylated fattyesters or acids, or mixtures thereof to form a polyester polyol.

In another alternate embodiment, the present disclosure provides aprocess comprising reacting a recycle stream selected from recycled PETcarpet, recycled PET bottles, recycled PET textiles, other recycled PETarticles, or mixtures thereof, with a glycol in a reactor, therebyforming a digested intermediate comprising polyols and contaminantsselected from colorants, dyes, pigments, inorganic fillers, undigestedpolymers or mixtures thereof. Then, the digested intermediate is reactedwith a hydrophobe selected from dimer fatty acids, trimer fatty acids,oleic acid, ricinoleic acid, tung oil, corn oil, canola oil, soybeanoil, sunflower oil, bacterial oil, yeast oil, algae oil, castor oil,triglycerides or alkyl carboxylate esters having saturated orunsaturated C₆-C₃₆ fatty acid units, saturated or unsaturated C₆-C₃₆fatty acids, alkoxylated castor oil, saturated or unsaturated C₉-C₁₈dicarboxylic acids or diols, cardanol-based products, recycled cookingoil, branched or linear C₆-C₃₆ fatty alcohols, hydroxy-functionalmaterials derived from epoxidized, ozonized, or hydroformylated fattyesters or acids, or mixtures thereof, thereby forming a polyesterpolyol.

In still another alternative embodiment, the present disclosure providesa process comprising reacting a recycle stream comprising bales of PETcontainers with a glycol in a reactor, thereby forming a digestedproduct stream comprising polyols, and at least one undigested stream.Then the digested product stream is reacted in the reactor with amodifier selected from C₃-C₈ dicarboxylic acids, their mono or dialkylesters, mono or dialkenyl esters, or anhydrides, thereby forming apolyester polyol.

In another alternate embodiment, the present disclosure provides apolyester polyol produced by a process comprising first reacting arecycle stream selected from recycled PET carpet, recycled PETcontainers, recycled PET textiles, other recycled PET articles ormixtures thereof, with a glycol in a reactor, thereby forming a digestedproduct stream comprising polyols, and at least one undigested stream.Then, the digested product stream is reacted in the reactor with ahydrophobe selected from dimer fatty acids, trimer fatty acids, oleicacid, ricinoleic acid, tung oil, corn oil, canola oil, soybean oil,sunflower oil, bacterial oil, yeast oil, algae oil, castor oil,triglycerides or alkyl carboxylate esters having saturated orunsaturated C₆-C₃₆ fatty acid units, saturated or unsaturated C₆-C₃₆fatty acids, alkoxylated castor oil, saturated or unsaturated C₉-C₁₈dicarboxylic acids or diols, cardanol-based products, recycled cookingoil, branched or linear C₆-C₃₆ fatty alcohols, hydroxy-functionalmaterials derived from epoxidized, ozonized, or hydroformylated fattyesters or acids, or mixtures thereof, thereby forming a polyesterpolyol.

In an embodiment, the present disclosure provides a process comprisingreacting recycled PET carpet fibers with a C₄ to C₃₆ mono alcohol toform a monomeric plasticizer.

In another alternate embodiment, the present disclosure provides aprocess comprising reacting recycled PTT carpet fibers with a C₄-C₃₆mono alcohol to form a monomeric plasticizer.

In still another alternate embodiment, the present disclosure provides aprocess comprising reacting a glycol selected from 1,3-propanediol,1,2-butylene glycol, 1,3-butylene glycol, 1,4-butanediol,2-methyl-1,3-propanediol, pentaerythritol, neopentyl glycol, glycerol,trimethylolpropane, 2,2,4,4-tetramethyl-1,3-cyclobutanediol,3-methyl-1,5-pentanediol, 1,4-cyclohexane-dimethanol,1,3-cyclohexanedimethanol, 1,6-hexanediol, tripropylene glycol,tetraethylene glycol, polyethylene glycols having a number averagemolecular weight up to about 400 g/mol, block or random copolymers ofethylene oxide and propylene oxide, and mixtures thereof with a recyclestream comprising recycled PTT carpet, thereby forming a product stream.

In another alternate embodiment, the present disclosure provides aprocess comprising reacting a recycle stream comprising recycled PTTcarpet with a C₄-C₃₆ alcohol to form a plasticizer.

In still another embodiment, the present disclosure provides a processcomprising first densifying a PET or PTT fiber recycle stream intopellets or granules. Then the densified PET or PTT fiber recycle pelletsor granules are reacted with a glycol in a reactor, thereby forming adigested product stream comprising a polyol product. Finally, the polyolproduct is filtered, thereby forming a filtered polyol product.

In another alternate embodiment, the present disclosure provides aprocess comprising first reacting a recycle stream comprising PETcontainers and densified PET or PTT-based carpet fibers in a reactorcomprising a mixer, thereby forming a digested product stream comprisingpolyols. Then the digested product stream is reacted in the reactor witha hydrophobe selected from dimer fatty acids, trimer fatty acids, oleicacid, ricinoleic acid, tung oil, corn oil, canola oil, soybean oil,sunflower oil, bacterial oil, yeast oil, algae oil, castor oil,triglycerides or alkyl carboxylate esters having saturated orunsaturated C₆-C₃₆ fatty acid units, saturated or unsaturated C₆-C₃₆fatty acids, alkoxylated castor oil, saturated or unsaturated C₉-C₁₈dicarboxylic acids or diols, cardanol-based products, recycled cookingoil, branched or linear C₆-C₃₆ fatty alcohols, hydroxy-functionalmaterials derived from epoxidized, ozonized, or hydroformylated fattyesters or acids, or mixtures thereof, thereby forming a polyesterpolyol.

BRIEF DESCRIPTION OF THE DRAWINGS

The subject matter of the present disclosure will be more fullyunderstood from the following detailed description, taken in connectionwith the accompanying drawings, in which:

FIG. 1 illustrates a flow diagram of a process to produce polyesterpolyols from recycled PET bottles.

FIG. 2 illustrates a flow diagram of a process to produce polyesterpolyols from recycled PET carpet.

FIG. 3 illustrates a flow diagram of a process to produce polyesterpolyols from a recycle stream of PET carpet, bottles, textiles andarticles where the digested stream is reacted with hydrophobes and/ormodifiers prior to separation of the contaminants.

FIG. 4 illustrates a flow diagram of a process to produce polyesterpolyols from a recycle stream of PET carpet, bottles, textiles andarticles where the digested stream is reacted with hydrophobes and/ormodifiers after separation of the contaminants.

FIG. 5 illustrates an integrated process for using recycled PET orPTT-based carpet to produce polyols that can be used in rigid foams,polyisocyanurate foams, polyurethane polymers, or flexible polyurethanefoams; monomeric plasticizers; polymeric plasticizers; recycled calciumcarbonate; quick lime; slaked lime; PET; or PTT in an environmentallyfriendly and energy efficient manner.

DETAILED DESCRIPTION OF THE INVENTION

The inventive process produces polyester polyols using a recycle streamof PTT or PET carpet, carpet fibers, yarn; PET containers, textiles,string, twine or other recycled PET or PTT articles.

Recycle Stream

The recycle stream treated in the inventive process can include recycledPTT carpet, recycled PET carpet, recycled PTT carpet fiber, recycled PETcarpet fiber, recycled PET yarn, recycled PTT yarn, recycled PETcontainers, recycled PET textiles, recycled PET twine or string, otherrecycled PET articles, or mixtures thereof. In each case, the recycledPET or PTT carpet, carpet fiber, yarn; PET containers, textiles, twineor string, or other recycled PET articles are post-industrial orpost-consumer materials. Preferably the recycled PET containers are PETbottles.

PET Bottles

When the recycle stream is PET bottles, the bottles typically originatefrom recycling centers where the recycled bottles are compressed intobottle bales that are typically held in place by baling wire, and aremounted on pallets for transportation. Periodically, pieces of wire canbreak off and become attached to the bale of bottles, thereby becomingpart of the recycle stream. Whole bottles are included in the bottlebales and are processed in the inventive process. This includes caps,liner and ring, the label on the bottle, the ink used to printinformation and graphics on the label, as well as the adhesive thatfastens the labels to the bottle. Caps are typically manufactured frompolyolefins such as polypropylene and polyethylene. The polyethylene istypically high density polyethylene (HDPE). The liner and ring aretypically manufactured from EVA, polyamide resin, or ethylene-propylenediene monomer (EPDM). Labels are typically produced from polypropylene,a polyamide resin or PET. The adhesive is typically a hot melt adhesiveor a pressure sensitive adhesive having a broad range of compositions.In one embodiment, the polyvinyl chloride (PVC) content of the recyclestream is less than 10,000 ppm based on the total weight of the recyclestream. Alternately, the PVC content is less than 1000 ppm or less than500 ppm based on the total weight of the recycle stream, or the recyclestream can be essentially free of PVC, where for the purposes of thisspecification, the term essentially free with regard to PVC in therecycle stream means less than 100 ppm PVC based on the total weight ofthe recycle stream.

Preferably, the recycle stream contains from 83.0 to 91.5 wt % PET,present as recycled PET bottles, 7.5 to 13.5 wt % polyolefins, 1.0 to3.0 wt % of an adhesives stream containing the adhesive material,polyamides and EPDM, and 0 to 0.5 wt % metals. Alternately, the recyclestream contains 84.0 to 90.0 wt % PET, 8.4 to 13.2 wt % polyolefins, 1.5to 2.5 wt % adhesive stream and 0.1 to 0.3 wt % metals.

Recycled PET & PTT Carpet

The recycle stream can include either a whole carpet stream or carpetfiber stream produced from PET or PTT. The whole carpet stream includesthe carpet fibers and contaminants such as the polyolefin-based backing,and adhesives such as rubber latex, SBR latex, carboxylated SBR latex,EVA emulsions, PVA emulsions and starches. SBR latex also typicallyincludes additives such as calcium carbonate extenders, surfactantfrothing agents, and polyacrylate thickeners. The carpet fiber streamincludes face fibers from the recycled carpet, and is typically composedof staple fibers or bulk continuous filament (BCF) fibers that have beenremoved from the whole carpet stream. Both the whole carpet and carpetfiber can further contain more contaminants such as dirt, pet hair, moldand the like, than a post-industrial recycle carpet stream, and mayrequire a washing step in conventional recycling schemes prior to use asa recycled PET or PTT stream.

When the recycle stream is PET or PTT carpet, the fibers typicallyoriginate as post-industrial off-grade, surplus or defective recyclecarpet, greige goods, or fiber products and post-consumer recyclecarpet. In the case of post-consumer recycled carpet, the carpet istypically collected by carpet installers for use as a recycle stream.

Recycled Polyurethane Flexible Foam

The recycled PET & PTT carpet stream may further contain recycledflexible polyurethane foam. Recycled polyurethane foam may be obtainedfrom post industrial or post consumer recycled carpet underlay. Thiscarpet underlay may be rebond polyurethane flexible foam or polyurethanerebond foam cut into sheets of various thickness from polyurethaneslabstock foam of various densities. Rebond polyurethane flexible foamis produced by adhering chunks of polyurethane flexible foam togetherusing an isocyanate prepolymer. The resulting rebond flexiblepolyurethane foam can have higher durability than a simple polyurethaneslabstock foam as a carpet underlay. Further, during the removal of PETor PTT carpet, the flexible polyurethane foam carpet cushion or underlayis frequently also removed. This polyurethane foam may be co-digestedwith PET & PTT by reacting the flexible polyurethane foam and the PET orPTT with glycol in a reactor with a mixer to form a digested productstream comprising polyol, as described above. The PET or PTT stream isselected from recycled PET or PTT-based carpet fibers, recycled PETbottle bale material, recycled PET or PTT fabric or fibers, or mixturesthereof. When PET or PTT-based carpet fibers are present, they havepreferably been densified. The co-digestion of the polyurethane foam andPET or PTT with glycol produces a polyester polyol. Another source ofrecycled polyurethane flexible foam includes post-industrial scrappolyurethane molded foam produced unintentionally during the productionof automotive seat cushions. Scrap flexible polyurethane foam resultingfrom the production of furniture and mattresses represents anotherpossible source of recyclable polyurethane foam suitable for thepractice of the novel process described herein. Finally, another sourceof flexible polyurethane foam includes scrap foam produced during theproduction of flexible slabstock foam.

Recycled PET & PTT Twine or String

When the recycle stream is recycled PET or PTT twine or string, postindustrial sources include the twine or string typically originatingfrom leftover or off-grade twine or string resulting from the productionof original twine or string. An additional post-industrial source ofstring includes excess or waste streams from manufacturers of nets andropes.

Other PET or PTT Recycled Articles

Other PET or PTT containing materials that can be recycled in theprocess of the present disclosure include recycled geotextiles, recycledfillings, such as toys, pillows, sofa and furniture cushioning,automotive fabric, wadding, and filtration media. Geotextiles arepermeable textile material used to increase soil stability, provideerosion control or aid in drainage. They are typically used inconstructing roads, pools and other construction projects. Fabricproduced from polyester staple fiber is used throughout the automotiveindustry in its fabrics because of its effectiveness and long life.Polyester staple fiber is also used in the wadding industry as a blendwith bi-component low melt fibers. Non woven fabrics are used for airfiltration, water filtration and oil filtration sectors.

Treatment of Recycled PET or PTT Carpet

The recycled PET or PTT carpet can be processed in a series of stepsprior to digestion. When the whole carpet is to be digested, the carpetcan be subjected to a size reduction step, where it is first cut,shredded or milled into pieces of reduced size suitable for the reactorused. Alternately, the carpet can be processed in conventional orwater-based size reduction systems. Such conventional size reductionsystems include, for example, a series of mechanical step(s) to reducethe size of the particles, including combinations of shredding andmilling step(s). An example of such a milling step is the use of ahammer mill. When the carpet fiber is to be digested, the whole carpetmust be subjected to a separation step where the carpet fibers areseparated from the carpet backing components of the whole carpet in aseries of mechanical steps. These steps can include the size reductionsystems described above, if required, followed by separation step(s)conducted in water or air using differences in density; e.g., with anair separator, centrifuge or other specific gravity-based air or aqueoussystems. Shaving, shearing or skiving can also be used to separate thecarpet fibers from the carpet backing. Following mechanical processingand separation, the processed stream may be treated in further stepsincluding washing, drying, and densification.

In one embodiment, the carpet components left over after separation fromthe fiber are then processed in a kiln, incinerator or gasifier tocombust the carpet backing to produce a combustion gas stream comprisingcarbon dioxide and acid gases, and a combusted solid streams containingcalcium carbonate, calcium oxide (quick lime), or calcium hydroxide(slaked lime) or mixtures thereof. Fuels to such combustion systemsinclude conventional, i.e., fossil-fuel based fuels, or bio-based fuels,such as wood, lignin, biodiesel, biobased butanol, biobased ethanol, oragricultural wastes. Other waste materials, such as municipal waste canbe combusted with the carpet backing. The combustion process istypically utilized as one part of a power generation process where theheat of combustion of the carpet backing is captured as steam producedin a boiler. The steam can then be converted to electricity in a steamturbine.

Washing

The separated, recycled PET or PTT carpet fibers can then be washed inone or more steps to remove contaminants such as dirt, hair and mold.Such methods include conventional techniques, e.g., slurrying the fiberswith a wash solution, optionally with agitation, followed by decantingand/or filtering the wash solution from the PET fibers. Filtration ofthe wash solution can be conducted using any conventional equipment,such as centrifugal filters, pressure filters or gravity filters.

Drying

The washed PET or PTT carpet fibers can then be dried in one or moresteps to reduce the moisture content. Drying equipment that can be usedfor the drying step include rotary dryers, drum dryers, belt dryers,vacuum dryers, bin dryers, tray dryers, tray dryers, fluidized beddryers, and trough dryers.

Densification

The main purpose for densification of the dried PET or PTT carpetfibers, as well as other fiber-based recycle stream such as yarn, twineor string, is to increase the bulk density of the resulting polymer suchthat the material may be conveniently fed into the reactor and also fitsinto the reactor much more efficiently. This allows the PET or PTTmaterial to be efficiently wetted by co-reactants that are introducedinto the reactor, thereby minimizing processing time. One method fordensifying the dried PET or PTT carpet fibers includes feeding thefibers, for example, via an auger or screw feeder, into either a twinscrew extruder or a single screw extruder to melt the fibers andsubsequently pelletize them. Conventional extrusion equipment can beused to perform such a densification. Another method for densifying thedried PET or PTT carpet fibers includes a friction densification systemthat utilizes a rotor and stator to soften the fibers to a point as tomake long agglomerated strands which are subsequently fed into agranulator to produce densified granules. Various types of agglomerationprocesses exist today. Two such examples are Herbold Meckesheim USA andPallman Industries.

Still another method for densifying the dried PET or PTT carpet fibersincludes simply heating the fibers to melt them, for example, byconveying the carpet fibers through an oven or other heat source using aconveyor belt. The melted fibers shrink and adhere to one another, thusyielding an increased bulk density feedstock that may then be granulatedor comminuted. This method avoids the need for relatively expensivepelletization and extrusion equipment.

Yet another method for densifying the dried PET or PTT fibers is via theintroduction of the fibers into an agglomerator or densifier apparatus.An agglomerator or densifier is essentially a large drum where severalblades spin at high speed near the bottom of the drum the bottom of thedrum, thereby creating friction until the material reaches its softeningpoint and densifies. The operator then adds water to cool the batchdown, and after the water evaporates, a discharge door is opened,releasing material that is frequently called PET or PTT popcorn orgranules. This type of agglomeration is typically referred to as “TubDensification.”

The bulk densities of the densified recycle PET material typicallyranges from 200 to 1,000 g/L as measured by determining the weight andvolume of a given quantity of densified material and dividing theresulting weight measured by the resulting volume measured. Preferably,the densified bulk densities can range from 400 to 1,000 g/L, morepreferably, 600 to 1,000 g/L. Bulk densities for other non-densifiedmaterials include recycled PET flakes of 250 to 450 g/L and recycled PETpellets of 750 to 950 g/L.

The fiber recycle stream can be obtained by the recycling processesdescribed above from post-industrial or post-consumer carpet backingprior to densification. The fiber recycle stream can also be obtained bycutting the fiber from industrial rolls prior to densification. Finally,the fiber recycle stream can be obtained by separation of the fibersfrom industrial rolls by aspiration. The fiber recycle stream can alsocan be washed and dried to remove contaminants prior to densification.Preferably, the fiber recycle stream yields a polyol product having aviscosity at 80° C. of less than 20,000 cP.

Recycled PET and Fabric or Textile

When the recycle stream is PET textile or fabric, the material typicallyoriginates as post-industrial off-grade or scrap, and can containpigments, dyes and other contaminants. About 65-70 percent of globalpolyester production is used for textiles, of which more than 65 percentis produced in China. The majority of the remaining 30-35 percent isused in the manufacture of PET beverage bottles. Post-industrialoff-grade fabric or textiles might originate from incorrectly dyedfabric or incorrectly woven textiles. Post-industrial scrap canoriginate from leftover fabric that results from cutting fabric duringthe manufacture of clothing, furniture, fabrics, shoes, curtains, andother articles that use PET. Post-consumer recycling of PET fabrics ortextiles can occur by utilizing worn-out polyester clothing from appareland uniform manufacturers and retailers as well as government agencies,hospitals and clinics, schools, sports clubs, and other entities.

Recycled PET Yarn

When the recycle stream is PET yarn, the material typically originatesas post-industrial off-grade or scrap, and can contain pigments, dyesand other contaminants. The recycled PET yarn can be present as materialwound about tubes or cones, some of which can be made from cardboard orplastic. Post-industrial off-grade or scrap might originate from carpetmanufacturing when a run of a particular carpet is completed, andpartially used cones or tubes with relatively small amounts of yarnremaining on the rolls, make it inefficient to begin another carpet runwith such a small amount of yarn on the cones or tubes. Such scrap mayalso result from off-grade yarn lots. The recycled PET yarn stream canfirst be processed by separating the yarn from the cardboard/paper orplastic tubes or cones. Examples of equipment capable of performing thisoperation include guillotines, roll splitters, reel splitters andupdrafts. The separated cardboard/paper tubes or cones can be reused,recycled as paper, or burned as fuel in an incinerator. The plasticcones or tubes are reusable by the manufacturer. The separated yarn canbe processed by densification as described above for PET yarn, carpetfibers, twine, string, fabric or textile. If extruded in the meltedstate, the PET yarn can be filtered to remove undesirable solidparticles prior to pelletization to form pellets that can be processedin the digestion reactors.

The carpet backing resulting from separating the PET or PTT carpetfibers from the whole carpet may be recycled into molded thermoplasticparts or incinerated for fuel value. The polyols resulting from thedigestion process of the carpet fibers may be filtered, treated withfiltration media such as celite or activated carbon to remove undigestedparticulates or color.

Mixed Recycle Streams

The recycle stream fed to the digestion reactor can be a mixture ofPET-containing or PTT-containing recycle sub-streams selected fromcarpet fibers, carpet, yarn; PET containers, textiles, twine or string.When the digestion reactor processes a mixture of PET or PTT-containingsub-streams, the reactor is equipped with a high speed, high shear mixeras discussed below. This is necessary to ensure breaking up the variousPET or PTT-containing solids. The mixed recycle stream can alternatelycontain polyethylene terephthalate or polytrimethylene terephthalate andpolyurethane flexible foam. These can be mixed and reacted in a reactorwith glycol in a process as described above to form a polyol.Preferably, the mixed recycle stream is selected from recycled PET orPTT-based carpet fibers, recycled PET bottle bale material, recycled PETbottles, recycled PET or PTT fabric or carpet fibers, or mixturesthereof. The mixed recycle stream can also preferably contain PET bottlebale material and densified mixtures of PET carpet fiber, PTT carpetfiber or mixtures thereof. These can be mixed and reacted in a reactorwith glycol in a process as described above to form a polyol.

Glycols

Glycols suitable for use are well known. By “glycol,” is meant a linearor branched, aliphatic or cycloaliphatic compound or mixture ofcompounds having two or more hydroxyl groups. Other functionalities,particularly ether or ester groups, may be present in the glycol. Inpreferred glycols, two of the hydroxyl groups are separated by from 2 to10 carbons, preferably 2 to 5 carbons. Suitable glycols include, forexample, ethylene glycol, propylene glycol, 1,3-propanediol,1,2-butylene glycol, 1,3-butylene glycol, 1,4-butanediol,2-methyl-1,3-propanediol, erythritol, pentaerythritol, neopentyl glycol,glycerol, trimethylolpropane, 2,2,4,4-tetramethyl-1,3-cyclobutanediol,3-methyl-1,5-pentanediol, 1,4-cyclohexane-dimethanol,1,3-cyclohexanedimethanol, diethylene glycol, dipropylene glycol,triethylene glycol, 1,6-hexanediol, tripropylene glycol, tetraethyleneglycol, polyethylene glycols having a number average molecular weight upto about 400 g/mol, block or random copolymers of ethylene oxide andpropylene oxide, and the like, and mixtures thereof. Preferably, theglycol is selected from propylene glycol, 2-methyl-1,3-propanediol,3-methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol,polyethylene glycol having a number average molecular weight of about200, and mixtures thereof. Propylene glycol is particularly preferred.In a preferred embodiment, the glycol is a recycled glycol, especiallyrecycled propylene glycol and recycled diethylene glycol. Propyleneglycol recovered from used deicing fluids is one example. In anotherpreferred embodiment, the glycol is a recycled ethylene glycol, whichmay be recovered from used engine antifreeze or coolant.

Hydrophobes

The polyols in the digested material are reacted with hydrophobes sothat the polyols can incorporate recurring units from at least one ofthe hydrophobes. The polyols in the digested material can be reactedwith the hydrophobe either before or after the undigested contaminantshave been separated from the polyols. The hydrophobes are reacted in thereactor in an amount within the range of 0.1 to 3.0, preferably 0.1 to1.0 moles of hydrophobe per mole of recycled PET bottle. Alternately,the hydrophobe is reacted in an amount within the range of 0.15 to 0.8moles of hydrophobe per mole of recycled PET bottle.

Suitable hydrophobes for use in the inventive processes are selectedfrom dimer fatty acids, trimer fatty acids, oleic acid, ricinoleic acid,tung oil, corn oil, canola oil, soybean oil, sunflower oil, bacterialoil, yeast oil, algae oil, castor oil, triglycerides or alkylcarboxylate esters having saturated or unsaturated C₆-C₃₆ fatty acidunits, saturated or unsaturated C₆-C₃₆ fatty acids, alkoxylated castoroil, saturated or unsaturated C₉-C₁₈ dicarboxylic acids or diols,cardanol-based products, recycled cooking oil, branched or linear C₆-C₃₆fatty alcohols, hydroxy-functional materials derived from epoxidized,ozonized, or hydroformylated fatty esters or acids, or mixtures thereof.

Preferably, the hydrophobe is selected from dimer fatty acids,ricinoleic acid, corn oil, canola oil, soybean oil, sunflower oil,bacterial oil, yeast oil, algae oil, castor oil, triglycerides or alkylcarboxylate esters having saturated or unsaturated C₆-C₃₆ fatty acidunits, saturated or unsaturated C₆-C₃₆ fatty acids, alkoxylated castoroil, saturated or unsaturated C₉-C₁₈ dicarboxylic acids or diols;cardanol-based products, recycled cooking oil, hydroxy-functionalmaterials derived from epoxidized, ozonized, or hydroformylated fattyesters or acids, or mixtures thereof. More preferably, the hydrophobe isselected from dimer fatty acids, ricinoleic acid, corn oil, canola oil,soybean oil, castor oil, triglycerides or alkyl carboxylate estershaving saturated or unsaturated C₈-C₂₀ fatty acid units, saturated orunsaturated C₈-C₂₀ fatty acids, alkoxylated castor oil, saturated orunsaturated C₉-C₁₈ dicarboxylic acids, cardanol-based products,hydroxy-functional materials derived from epoxidized, ozonized, orhydroformylated fatty esters or acids, or mixtures thereof.

Modifiers

Modifiers can also be included in the inventive process, to increase themolecular weight of the polyols in the digested material without overlyincreasing the viscosity. The polyols in the digested material can bereacted with the modifier either before or after the undigestedcontaminants have been separated from the digested material. They canalso be used with or without the hydrophobes as described above, and areselected from C₃-C₈ dicarboxylic acids, their mono or dialkyl esters,mono or dialkenyl esters, diesters, or anhydrides. Preferably, themodifier is selected from alkyl ester, anhydride or free acidderivatives of glutaric acid, adipic acid, succinic acid, malonic acidcyclohexane dicarboxylic acids, maleic acid, fumaric acid, itaconicacid, phthalic acid, 2,5-furandicarboxylic acid, isophthalic acid, ormixtures thereof. More preferably, the modifier is selected from alkylester, anhydride or free acid derivatives of adipic acid, maleic acid,succinic acid, itaconic acid, phthalic acid, isophthalic acid, and2,5-furandicarboxylic acid. When used with hydrophobes, the modifierscan be reacted simultaneously with the hydrophobe or sequentially inmultiple steps before or after the hydrophobe.

Polyisocyanates

Polyisocyanates suitable for use in the inventive process includearomatic, aliphatic, cycloaliphatic polyisocyanates, and trimerderivatives thereof, prepolymers thereof, carbodiimide derivativesthereof, blocked derivatives thereof and blends thereof. Examplesinclude toluene diisocyanates (TDIs), methylene bisphenyl diisocyanates(MDIs), polymeric MDIs, naphthalene diisocyanates (NDIs), hydrogenatedMDIs, trimethyl- or tetramethylhexamethylene diisocyanates (TMDIs),hexamethylene diisocyanate (HDI), hexamethylene diisocyanate trimer,isophorone diisocyanates (IPDIs), isophorone diisocyanate trimer,cyclohexane diisocyanates (CHDIs), xylene diisocyanates (XDI),hydrogenated XDIs, and the like. Aliphatic diisocyanates, such ashexamethylene diisocyanate and isophorone diisocyanates are particularlypreferred. The polyisocyanates can be reacted with the polyester polyoleither before or after the undigested contaminants have been separatedfrom the polyester polyol. The polyisocyanates can also be reacted withthe digested polyols, independently of whether the digested polyols haveor will be reacted with hydrophobes or modifiers.

Digestion Reaction

When the recycle stream is PET bottles, the recycled PET bottles,polyolefins, and contaminants from the recycle stream and glycol areplaced in a reactor. The contaminants can include unfinished soft drinkresidues, food residues such as mustard and ketchup, paper labels,aluminum, dirt, oddly colored PET, broken glass, wood, adhesives, sealmaterials, ferromagnetic particles, polyvinyl chloride, pigmented andcrystallized PET (C-PET), un-separated trash, non-PET recycle streams,polystyrene, glycol-modified PET (PETG). Multilayer PET containers mayalso include ethylene/vinyl alcohol (EVOH) copolymers, interlayerthermoplastic adhesives, metallized labels, and extrusion-blown PET(E-PET) containers. Other PET or PTT recycle streams or mixtures ofstreams can be placed in the reactor, including carpet, carpet fiber,textile, yarns, twine, string, as described above. When mixtures of therecycle streams are used, preferably, the mixtures contain PETcontainers and carpet or carpet fiber, whether PET or PTT based. Themixture can alternately contain PET bottle bale material, and PET or PTTcarpet fiber (or mixtures thereof). These mixtures can be reacted withglycol in a reactor with a mixer, as discussed above, to form a digestedproduct stream comprising a polyol. Unless otherwise specified, reactorconditions, glycol usage, catalyst, and equipment used in the digestionof mixed streams is as discussed in the general procedure below.

Reactor

The reactor can generally be any closed or closeable vessel suitable forholding, mixing and reacting the reactor contents at the temperaturesand pressures of the reaction. The materials of construction for thereactor may also be any consistent with the reactants and reactorproducts from a chemical compatibility standpoint, as well as from atemperature/pressure standpoint. For example, the reactor may beconstructed from carbon steel, stainless steel, Inconel, Hasteloy, andMonel. The reactor is typically a cylindrical vessel, oriented eitherhorizontally or vertically, with flat or dished heads. When dished headsare used, they can be ellipsoidal, torispherical, hemispherical orconical. The reactor is typically equipped with sufficient nozzles toallow injection of liquid reactants, draining of reactor products orcleaning, e.g., nozzles to allow steam cleaning. The reactor preferablyhas a discharge valve. Preferably, the discharge valve has maximumclearance when the valve is open, e.g., a ball valve. Preferably, thereactor is equipped with heating/cooling means that can include externaljacketing or internal coils. The heating/cooling media can includeconventional fluids such as steam, oil and water. Preferably, thedischarge valve is jacketed to allow heating and cooling.

The reactor can be operated in configurations designed to disperse theundigested polyolefin phase or to allow the undigested material toagglomerate. When it is desired to disperse the undigested polyolefinphase, or alternately, when mixtures of recycle streams are used in thedigestion reactor, e.g., PET containers and densified carpet fibers, thereactor is typically equipped with at least one mixer having a motor,rotating shaft and an impeller. Preferably, the mixer is equipped withat least one high speed, high shear impeller for breaking up anddispersing solid and semi-solid pieces of the PET bottles, as well asfor dispersing undigested materials such as polyolefins in the volume ofglycol and digested material. The mixer can contain one or more shaftsto optimize the breakup, dispersion and mixing of solids in the reactorcontents. Preferably, the mixer contains one, two or three shafts.Preferably, the mixers employ open-disk impellers, closed rotatingrotor-stators, a rotor-stator with revolving stator, or a fixed rotorand stator. The tip speed of the at least one high speed, high shearimpeller is preferably 40 to 120 feet per second, more preferably 60 to100 feet per second. Low speed mixing and/or low shear impellers presentas the sole impeller, are not suitable for dispersion since they aremerely designed to prevent solids sedimentation in the vessel or toblend materials. The polyolefin material present in the reactor does notdigest, but softens. Without high levels of shear the softenedpolyolefin mass does not disperse, potentially presenting difficultseparation problems, requiring shutdown and manual cleaning. Thesoftened polyolefin mass can also wrap around and/or stick-to theagitator shaft, which also presents a difficult operational problem.

In certain embodiments of the invention, it is preferable to allow thenon-digested polyolefin phase to accumulate into a large mass, adheringto and collecting non-digested contaminants within the mass, separatingthe liquid polyol from the polyolefin and non-digested contaminants. Inthis case, low-speed, load sheer mixing equipment is typically used.These can be present in addition to, or instead of the high shear mixerpresent in the reactor, as described above. The polyolefin phasecontaining non-digested contaminants can then be recycled into otherapplications such as artificial wood. Surprisingly, small amounts ofadhesives such as ethylene/acrylic acid copolymers orethylene/methacrylic acid copolymers can be added to the reactionmixture, where it resides in the non-digested polyolefin phase,enhancing the ability of this phase to both agglomerate into a largemass, and to collect and adhere to non-digested contaminants, therebyfacilitating their separation from the polyol phase by decanting. It isbelieved that numerous other non-digesting adhesive materials can beadded to the reaction to provide this agglomeration effect, such aspolyvinyl acetate, polyvinyl alcohol, polyvinyl butyric, polyvinylformal, polyvinyl ether, acrylic polymers, polychloroprene,styrene-butadiene copolymers, styrene-diene-styrene copolymers,polyisobutylene, acrylonitrile-butadiene, polyurethane thermoplastics,co- and ter-polymers of ethylene with vinyl acetate, ethyl acrylate,butyl acrylate, methyl acrylate, acrylic acid and combinations thereof.

The ethylene/acrylic acid or ethylene methacrylic acid co- orterpolymers preferably include between 3 and 50 wt. % (meth)acrylic acidcomonomer by weight, and may include other ter-monomers such as alkyl(meth)acrylates, vinyl acetate, maleic anhydride, maleic acid, alkylesters of maleic acid, free-radically polymerizable comonomers, andmixtures thereof. Further, the ethylene/acrylic acid or ethylenemethacrylic acid co or terpolymers as described above may be partiallyor completely neutralized as metal salts to form ionomers. Examples ofsuch ionomer products include DuPont Surlyn™ products, DuPont Elvaloy™products and Dow Chemical Amplify™ products.

Emulsifiers

An emulsifier can optionally be used to aid in the dispersion of thepolyolefin material. Such an emulsifier typically contains ananhydride-, epoxide-, carboxylic acid- or ester-containing polymer or amixture thereof. Preferably, the emulsifier is selected fromstyrene/maleic anhydride copolymers, ethylene/acrylic acid copolymers orterpolymers, ethylene/methacrylic acid copolymers or terpolymers, metalsalts of ethylene acrylic acid copolymers or terpolymers, metal salts ofethylene/methacrylic acid copolymers or terpolymers, ethylene/alkylacrylate copolymers or terpolymers, ethylene/glycidyl acrylatecopolymers or terpolymers, or ethylene/glycidyl methacrylate copolymersor terpolymers. Preferably, the metal of the metal salts ofethylene/(meth)acrylic acid copolymers or terpolymers is selected fromzinc or sodium.

In the digestion, the recycle stream and glycol are heated within therange of 80° C. to 260° C., alternately 100° C. to 250° C., 130° C. to240° C., or 160° C. to 230° C., optionally in the presence of acatalyst, to form a digested stream and a non-digested stream.Typically, the reaction is run at atmospheric pressure, although thereaction can be run at pressures between about 0 psia to about 100 psia,about 5 psia to about 75 psia, or about 7 psia to about 65 psia. Inthose instances where it is desirable to remove water, reduced pressuresbelow 1 atmosphere can be useful. The digested stream comprises glycol,bis(hydroxyalkyl)terephthalates, and oligomers thereof. Undigestedmaterial includes polyolefins, dyes, inorganic fillers and othercontaminants.

Catalyst

A catalyst can be used in the digestion reaction. In particular,suitable catalysts comprise tin, titanium, zinc, antimony, germanium,zirconium, or manganese. Specific examples include titanium alkoxides(e.g., tetrabutyl titanate or tetraisopropyl titanate), titanium(IV)phosphate, titanium(IV) tetrabutoxide, titanium (IV) tetrapropoxide,zirconium alkoxides, zinc acetate, manganese(II) acetate, antimonytrioxide, germanium oxide, or the like, and mixtures thereof. Catalyststhat do not significantly promote isocyanate reaction chemistries arepreferred. Preferably, the catalyst is butyltin hydroxide oxide hydrateor a titanium alkoxide such as titanium t-butoxide. The amount ofcatalyst used is typically in the range of 0.005 to 2 wt. %, based onthe total amount of polyol being prepared. Alternately, the amount ofcatalyst used is in the range of 0.01 to 1 wt. %, 0.02 to 0.7 wt. %, or0.05 to 0.2 wt. %, based on the total amount of polyol being prepared.

Usually, the digestion reaction is performed by heating the recycledmaterial, e.g., PTT or PET carpet, carpet fibers, yarn; PET containers,textiles, string, twine or other recycled PET or PTT articles;glycol(s); and any catalyst at least until the mixture liquefies andparticles of the PET are no longer apparent. Reaction times range fromabout 30 minutes to about 16 hours, more typically 1 to 10 hours, evenmore typically 3 to 8 hours, depending on the reaction temperature,source of the PET or PTT, the particular glycol reactant used, mixingrate, desired degree of depolymerization, and other factors that arewithin the skilled person's discretion.

The molar ratio of glycol to PET (or PTT) from the recycle stream is atleast 0.8, preferably 1.0 to 6.0, more preferably 2.5 to 4.5. When theglycol/PET (or PTT) molar ratio is below 0.8, the hydrophobe-modifiedpolyester products are often too hard to be digested. On the other hand,when the glycol/PET (or PTT) molar ratio is greater than about 6, thehydroxyl numbers tend to exceed the practical upper limit of about 800mg KOH/g.

The digested material can be reacted in a further step with one of theparticular hydrophobes described above to give a polyester polyol. Thereaction between the digested stream and the hydrophobe is performedunder conditions effective to promote one or more of several differentpossible reactions between the digested intermediate and the hydrophobe,principally condensation reactions. For instance, hydroxyl groups in thedigested intermediate can react with acid or ester groups in thehydrophobe to generate esters from the acids or new esters from theoriginal ones. Because the hydrophobes often have hydroxyl functionalityas well, new esters can be formed that utilize that hydroxylfunctionality. Other kinds of reactions may occur, includingcrosslinking or cycloaddition reactions involving carbon-carbon doublebonds and/or allylic hydrogens that were originally present in thehydrophobe.

Reactions between the digested stream and hydrophobe are typicallyperformed by heating at temperatures within the range of 80° C. to 260°C. Alternately, the temperature range is 90° C. to 230° C., 100° C. to220° C. or 110° C. to 210° C. Typically, the reaction is run atatmospheric pressure, although the reaction can be run at pressuresbetween about 0 psia to about 100 psia, about 5 psia to about 75 psia,and about 7 psia to about 65 psia. When it is desirable to remove water,the reactor is preferably operated under vacuum, e.g., 0 psia to lessthan 14.7 psia, or alternately 5 psia to less than 14.7 psia, or 0 psiato 7 psia. Water generated in the reaction is normally removed from thereaction mixture as it forms. This is typically performed by vacuumstripping, wiped-film evaporation, sparging with dry air or nitrogen,and the like. The reaction is normally continued until a pre-determinedamount of water has been collected or a target acid number and/orhydroxyl number is reached for the product.

The amount of hydrophobe incorporated into the polyol is within therange of 3 to 70 wt. %. Alternately, the amount of hydrophobe in thepolyol is 4 to 60 wt. % or 5 to 55 wt. %. When less than 3 wt. % ofhydrophobe is used, there is too little benefit from including it interms of generating useful polyols (for instance, the hydroxyl numbersmay reach or exceed their useful upper limit). When more than 70 wt. %of the hydrophobe is used, formulation cost may be higher thandesirable, and there is usually little or no additional performancebenefit.

In another embodiment, the polyester polyol can be made in a single stepby reacting the recycled PTT or PET carpet, carpet fibers, yarn; PETcontainers, textiles, string, twine or other recycled PET or PTTarticles or combinations thereof in the recycle stream, glycol, andhydrophobe under conditions effective to produce the polyol. As withpolyols made using the two-step process, the molar ratio of glycol toPET (or PTT) is at least 0.8, the amount of hydrophobe reacted into thepolyol is within the range of 3 to 70 wt. %, the resulting polyol has anaverage hydroxyl functionality within the range of 1.8 to 2.7 and ahydroxyl number within the range of 25 to 800 mg KOH/g. When thesingle-step process is used, it is preferred to utilize a reflux systemthat returns condensed glycols to the reactor while allowing removal ofwater, as removal of too much glycol can result in cloudy or opaquepolyols. Reaction temperatures in the single step process are asdescribed above for the two-step process. Preferably, a two-step processis used.

The polyester polyols produced by the inventive processes have hydroxylnumbers within the range of 25 to 800 mg KOH/g, preferably 35 to 500 mgKOH/g, more preferably 40 to 400 mg KOH/g. Hydroxyl number can bemeasured by any accepted method for such a determination, including,e.g., ASTM E-222 (“Standard Test Methods for Hydroxyl Groups UsingAcetic Anhydride Acetylation”). The polyols also have average hydroxylfunctionalities (i.e., the average number of —OH groups per molecule)within the range of 1.8 to 2.7, preferably 2.0 to 2.5.

In some embodiments, the polyester polyols produced in the inventiveprocess are flowable liquids at temperatures of 25 to 100° C., and haveviscosities measured at 25° C. less than 100,000 cP, more preferablyless than 30,000 cP, most preferably less than 20,000 cP. A preferredrange for the polyol viscosity is 100 to 10,000 cP, more preferably 500to 5,000 cP. Viscosity can be determined by any industry-acceptedmethod. It is convenient to use, for instance, a Brookfield viscometer(such as a Brookfield DV-III Ultra rheometer) fitted with an appropriatespindle, and to measure a sample at several different torque settings toensure an adequate confidence level in the measurements.

The polyols produced by the inventive processes preferably have low acidnumbers. Low acid numbers can be ensured by driving reactions throughremoval of water from the reaction mixture to the desired level ofcompletion. Preferably, the polyols have an acid number less than 30 mgKOH/g, more preferably less than 10 mg KOH/g, and most preferably lessthan 5 mg KOH/g. Acid numbers can be adjusted if necessary for aparticular application with an acid scavenger such as, for example, anepoxide derivative, and this treatment can be performed by themanufacturer, distributor, or end user.

In another embodiment, the current subject matter provides a processcomprising reacting a recycle stream selected from recycled PET carpet,recycled PET carpet fiber, recycled PET bottles, recycled PET textiles,recycled PET articles, or mixtures thereof, with a glycol in a reactor,thereby forming a digested intermediate comprising polyols andcontaminants selected from colorants, dyes, pigments, inorganic fillers,undigested polymers or mixtures thereof. The digested intermediate canbe further reacted with a polyisocyanate to form a polyurethane, apolyisocyanurate, or an isocyanate terminated prepolymer. The digestedintermediate can also be reacted with a hydrophobe selected from dimerfatty acids, trimer fatty acids, oleic acid, ricinoleic acid, tung oil,corn oil, canola oil, soybean oil, sunflower oil, bacterial oil, yeastoil, algae oil, castor oil, triglycerides or alkyl carboxylate estershaving saturated or unsaturated C₆-C₃₆ fatty acid units, saturated orunsaturated C₆-C₃₆ fatty acids, alkoxylated castor oil, saturated orunsaturated C₉-C₁₈ dicarboxylic acids or diols, cardanol-based products,recycled cooking oil, branched or linear C₆-C₃₆ fatty alcohols,hydroxy-functional materials derived from epoxidized, ozonized, orhydroformylated fatty esters or acids, or mixtures thereof, a modifieror both a hydrophobe and modifier to form polyester polyols as describedabove. When the digested intermediate is reacted with both a hydrophobeand modifier, the hydrophobe and modifier can either be reactedsequentially with the digested intermediate in any order, orsimultaneously. The hydrophobes and modifiers are as described above.

The digested intermediate can be processed in a solid-liquid separationstep to separate the contaminants from the contaminants-free polyesterpolyol. The solid-liquid separation can be conducted using theseparations described above: filtration, centrifugation, decantation,flotation, flocculation and sedimentation or combinations thereof.

In one embodiment, where it is desirable to maintain a homogeneousdispersion of contaminants in the polyol, and thereby prevent them fromseparating, it is preferred that the resulting polyol have a high enoughviscosity during storage and shipping such that the dispersedcontaminants do not separate by either flotation (for example, theundigested polymer such as a polyolefin or a styrene/butadiene adhesive)or settling (for example, the inorganic fillers). This approach avoidsthe need for a solid/liquid separation step, and permits the recycle ofall components present in the resulting polyol, including thecontaminants. Thus, polyols in the digested intermediate preferably havea viscosity greater than 10,000 cps at 50° C., more preferably greaterthan 20,000 cps at 50° C., and most preferably having a viscositygreater than 30,000 cps at 50° C.

In another alternate embodiment, the current subject matter provides apolyester polyol composition comprising: (i) recurring molecular unitsobtained from a recycled polymer source selected from recycled PETcarpet, recycled PET containers, recycled PET textiles, recycled PETarticles or mixtures thereof; (ii) a glycol; and (iii) a contaminantcomprising undigested particles of polyolefin and undigested particlesof adhesive. The polyester polyol composition can also include: (iv) atleast one contaminant selected from colorants, dyes, pigments andinorganic fillers, and/or a hydrophobe, a modifier or mixtures thereof.Preferably, the PET containers are PET bottles from a bottle bale.

In still another alternate embodiment, the present disclosure provides apolyester polyol composition comprising (i) a digested intermediateobtained from a recycled polymer source selected from recycled PETcarpet, recycled PET carpet fiber, recycled PET bottle bases, recycledPET textiles, other recycled PET articles, or mixtures thereof; (ii) aglycol; and (iii) at least one of a C₃-C₈ dicarboxylic acid and ahydrophobe selected from dimer fatty acids, trimer fatty acids, oleicacid, ricinoleic acid, tung oil, corn oil, canola oil, soybean oil,sunflower oil, bacterial oil, yeast oil, algae oil, castor oil,triglycerides or alkyl carboxylate esters having saturated orunsaturated C₆-C₃₆ fatty acid units, saturated or unsaturated C₆-C₃₆fatty acids, alkoxylated castor oil, saturated or unsaturated C₉-C₁₈dicarboxylic acids or diols, cardanol-based products, recycled cookingoil, branched or linear C₆-C₃₆ fatty alcohols, hydroxy-functionalmaterials derived from epoxidized, ozonized, or hydroformylated fattyesters or acids, or mixtures thereof.

In another alternate embodiment, the present disclosure provides apolyester polyol composition comprising: (i) a digested intermediateobtained from a recycled polymer source selected from recycled PETcarpet, recycled PET carpet fibers, recycled PET bottle bales, recycledPET textiles, other recycled PET articles or mixtures thereof; (ii) aglycol; and (iii) at least one of a C₃-C₈ dicarboxylic acid and ahydrophobe selected from dimer fatty acids, trimer fatty acids, oleicacid, ricinoleic acid, tung oil, corn oil, canola oil, soybean oil,sunflower oil, bacterial oil, yeast oil, algae oil, castor oil,triglycerides or alkyl carboxylate esters having saturated orunsaturated C₆-C₃₆ fatty acid units, saturated or unsaturated C₆-C₃₆fatty acids, alkoxylated castor oil, saturated or unsaturated C₉-C₁₈dicarboxylic acids or diols, cardanol-based products, recycled cookingoil, branched or linear C₆-C₃₆ fatty alcohols, hydroxy-functionalmaterials derived from epoxidized, ozonized, or hydroformylated fattyesters or acids, or mixtures thereof. Preferably, the polyester polyolcomposition contains both a C₃-C₈ dicarboxylic acid and a hydrophobe.

Comminution of Recycle Stream

The recycle waste stream can undergo a comminution step to break up therecycled bottles, carpet or other recycled PET or PTT material asdescribed above, prior to contact with glycol and the digestion step.Comminution of the recycled stream produces fragments that take up lessvolume in the digestion reactor, as well as exposing more surface areafor reaction. Such comminution can be conducted via grinding, cuttingand shredding or combinations thereof. Grinding involves the applicationof compression, impact or shear, where the magnitude of the forceapplied and the duration of the application affect the degree of solidsbreakup. Grinding equipment that can be used includes jaw crushers,gyratory crushers, shredders, hammer mills, fixed head mills, platemills, roller mills, ball mills, and edge runner mills. Cuttingequipment can include vessels using rotating knives, such as a bowlchopper. Shredding equipment includes chippers and single or multi-shaftshredders. Examples of companies that supply suitable comminutionequipment for carpet include SSI Shredding Systems, Inc.; UniversalRefiner Corporation; TANA Oy (Finland); and Vecoplan LLC. Examples ofcompanies that supply suitable comminution equipment for PET bottlesinclude WEIMA America, Inc.; Vecoplan LLC; Jaydeep Engineering (India);Jordan Reduction Solutions; Recycling Equipment, Inc.; Forrec RecyclingSystems (Italy); and Cresswood Shredding Machinery.

The comminution step can be conducted in a vessel separate from thedigestion reactor or in the digestion reactor, provided that comminutionproceeds prior to contact with glycol and the digestion reactor usingits mixer. Typically, comminution is conducted at temperatures of from−10 to 45° C., and decreases the size of the recycled PET or PTTcontaining material digested in the digestion reactor to between 0.1 mmand 40 mm.

Metals Separation

Metals are separated from the recycle stream to minimize contaminationwith downstream products, and to prevent downstream processingdifficulties. Magnetic (magnetically susceptible) metals include iron,cobalt, nickel, and steel; non-magnetic, weakly magnetic or inductionfield detectable metals include stainless steel, lead, chrome, zinc,copper, tin and aluminum. The magnetically susceptible material oftenincludes wire from the bales of PET bottles, but it can also includeun-separated metallic trash or other contaminants.

In one embodiment, the metals separation includes a metal detector thatanalyzes the recycle stream to detect the presence of a metal, forexample, as it passes proximate to the detector. When metal is found, itcan be removed from the recycle stream, either manually, or through asystem that operates automatically. Such automatic systems include, forexample, a conveyor that transports the recycle stream past the metaldetector. Upon detection of metal, the metal can be removed from therecycle stream using a blast of air or other gas, employing a mechanicaldevice to push or displace the material out of the primary flow of therecycle stream, or the conveyor itself can alter its pathway to removethe metal, e.g., a section of the conveyor can retract to allow materialto drop into a rejection vessel. Preferably, the metals separation stepproduces a stream containing less than 1 wt % of metals.

The magnetic separation equipment can utilize either electromagnetic orpermanent magnets or induction field detectors, and can include drumseparators, drawer magnets, in-line magnets, including gravity in-linemagnets, plate magnets, including plate housing magnets or suspendedplate magnets, grate magnets, wedge magnets, or hump or half-humpmagnets.

Operation of the magnetic separators can either be batch, semi-batch orcontinuous. Prior to magnetic separation, the recycle stream can have aconcentration of magnetically susceptible material of from 0 to 5 wt. %.Following magnetic separation, the recycle stream will have aconcentration of less than 1 wt. %, alternately, less than 0.5 wt. %.

Polyolefin Separation

Polyolefins present in the waste recycle stream do not digest in theglycol. Instead, in certain embodiments they are dispersed intofragments using the high speed, high shear mixer and optionallyemulsifiers, to a particle size range from 100 nm to 11 cm, 0.5 mm to 11cm or 0.5 mm to 3 cm. The polyolefins and other contaminants can beseparated through liquid-solid separation steps selected fromfiltration, centrifugation, decantation, flotation, flocculation andsedimentation or combinations thereof. When the separation is performedby decanting, the digested/reacted liquid is drained, leaving theremaining polyolefin solids. The digested/reacted liquid can be pumpedto a storage vessel. The remaining polyolefin solids can be furtherprocessed. For example, the solids may be rinsed, dried and extrudedinto fibers or pellets. During extrusion, various additives, such ascompatibilizers, antioxidants, fillers, fibrous or platelet reinforcingagents, stabilizers or colorants can be added.

When the liquid-solid separation is performed by decanting, thetemperature of the separation step can range from the digestion/reactiontemperatures to room temperature, i.e., from 20 to 100° C. Alternately,the separation can be conducted at temperature ranges of from 50 to 100°C. or 60 to 90° C.

The separation can also be performed by filtration or centrifuging. Whenthe separation is performed by filtration, the filtration can either begravity filtration through screens or belt filters using conventionalseparation media, or pressure filtration through plate and frame orpressure filters. As with separation by decanting, the recoveredpolyolefin solids can then be extruded as described above.

In certain embodiments of the present subject matter, it is preferableto allow the non-digested polyolefin phase to accumulate into a largemass, adhering to and collecting non-digested contaminants within themass, and then separating the liquid polyol from the polyolefin andnon-digested contaminants. The polyolefin phase containing non-digestedcontaminants can then be recycled into other applications such asartificial wood. Surprisingly, small amounts of adhesives such asethylene/acrylic acid copolymers or ethylene/methacrylic acid copolymerscan be added to the reaction mixture. Such adhesives exit the reactionsystem with the non-digested polyolefin phase, which enhances theability of this phase to both agglomerate into a large mass, and theability to collect and adhere to non-digested contaminants, therebyfacilitating their separation from the polyol phase by decanting. It isbelieved that numerous other non-digesting adhesive materials can beadded to the reaction to provide this agglomeration effect, such aspolyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinylformal, polyvinyl ether, acrylic polymers, polychloroprene,styrene-butadiene copolymers, styrene-diene-styrene copolymers,polyisobutylene, acrylonitrile-butadiene, polyurethane thermoplastics,co- and ter-polymers of ethylene with vinyl acetate, ethyl acrylate,butyl acrylate, methyl acrylate, acrylic acid and combinations thereof.In this case, the temperature of the separation step can range from thedigestion/reaction temperatures to room temperature, i.e., from 20 to230° C. Preferably, the separation can be conducted at lower temperatureranges, e.g., from 90 to 190° C.

Carbon Bed Filtration

A carbon bed can be used to remove some of the colorants present asorganic molecules in the polyester polyol, e.g., the source of thecolorants is typically the colored caps or tinted bottles that may bepresent in the recycle PET bottles or other PET or PTT based recyclematerials.

The digested intermediate is treated with activated carbon underconditions effective to give a polyester polyol with reduced color andmeasured by the color index. Color index is defined by 100×(|a*|/L*) asmeasured by CIE colorimetric analysis. The carbon-treated polyol willhave a higher value, usually a low negative value. The absolute value ofa* (i.e., |a*|) is used to compute the color index using the aboveformula. Any suitable means can be used to perform the colorimetricanalysis via transmission through the liquid polyol. It is convenient tomeasure transmission spectral properties using a spectrophotometer suchas a Cary® 100 Conc UV/vis spectrophotometer (Varian), an X-Rite color8200 spectrophotometer, an X-Rite color i7 spectrophotometer, or similarequipment.

Activated carbon comes in many suitable forms, and the form actuallyused will depend on reactor design, process scale, the nature of thedigested intermediate to be treated, and other factors. The activatedcarbon is normally produced from carbonaceous sources such as nutshells,coconut husks, peat, wood, coal, or other sources. Raw material istypically activated and/or carbonized chemically by treatment withacids, bases, or salts at temperatures up to about 900° C. Thereafter,it may be carbonized and/or oxidized by heating either in the presenceor absence of an oxygen-containing gas (e.g., air or steam) at 600° C.or higher. A combination of treatments can be used. Suitable activatedcarbons are supplied as powders, granules, beads, extrudates, or otherforms. Preferably, the activated carbon has a surface area greater than300 m²/g, more preferably greater than 500 m²/g. A preferred range forthe surface area is 500 m²/g to 2000 m²/g. Suppliers include, forexample, Paro Chemical, Jacobi Carbons, Calgon Carbon, Norit Americas,and many others.

The amount of activated carbon needed will depend on the source of therecycled material, the treatment unit design, temperature, the degree ofcolor reduction needed, and other factors. Preferably, the activatedcarbon is used in an amount within the range of 0.1 to 10 wt. %, morepreferably 0.5 to 5 wt. %, based on the amount of digested intermediateto be treated.

The carbon treatment is preferably performed by combining a warm or hot(30° C. to 180° C., preferably 45° C. to 150° C., most preferably 50° C.to 120° C.) digested material with the activated carbon, mixing untilhomogeneous, and allowing the carbon and digested intermediate to remainin contact for several minutes to several hours, preferably from 10minutes to 4 hours. It is convenient to simply stir the carbon-treatedintermediate at the desired temperature for the duration of thetreatment.

Following treatment with activated carbon, the digested recycledmaterial is filtered, optionally using a filter aid such as diatomaceousearth (e.g., Celite® 545), molecular sieves, clays, inorganic oxides(aluminas, silicas, silica-aluminas, magnesium silicates, etc.), or thelike. Diatomaceous earth is particularly preferred. Filtration,especially when using a filter aid, removes the activated carbon,impurities adsorbed by the activated carbon, undigested PET or PTTparticles, and other insoluble material including residual plastics,metal, paper, or other impurities. Heat, pressure, recirculation throughthe filtration medium to effectively produce multiple filtrations, orsome combination of these may be used to reduce filtration time orimprove results. It may be desirable, for instance, to pre-heat thefilter and/or polyol before use and to perform the filtration in thepresence of heat to reduce viscosity and enhance process efficiency.Additionally, it may be desirable to perform multiple filtrations toobtain a more highly purified polyester polyol. If desired, bleachingearths and bleaching clays can be used for reducing or lowering thecolor of the polyols, such as, e.g., F1 or F76, commercially availablefrom BASF.

The polyester polyols produced by the inventive process can be used toformulate a wide variety of polyurethane and polyisocyanurate products.By adjusting the proportion of hydrophobe used, a targeted degree ofpolyol hydrophobicity can be achieved. The ability to controlhydrophobicity is particularly valuable in the coatings industry. Thepolyols can be used for cellular, microcellular, and non-cellularapplications including flexible foams, rigid foams (includingpolyisocyanurate foams), urethane dispersions, coatings, adhesives,sealants, urethane acrylate derivative coatings, powder coatings, tankcoatings, and elastomers. The resulting polyurethanes andpolyisocyanurates are potentially useful for automotive andtransportation applications, building and construction products, marineproducts, packaging foam, flexible slabstock foam, carpet backing,appliance insulation, cast elastomers and moldings, footwear, biomedicaldevices, and other applications.

(Meth)Acrylate Derivatives

The polyester polyols obtained in the inventive process described abovecan be esterified with acrylic acid or methacrylic acid with thesimultaneous elimination of water to form (meth)acrylate derivatives.The reaction is typically conducted in the presence of an air or oxygenpurge at temperatures below about 140° C. and in the presence of a freeradical scavenger to avoid free radical polymerization of the(meth)acrylate functionality. Suitable free radical scavengers include,for example, phenothiazine, butylated hydroxyl toluene and1,4-hydroquinone at levels between about 0.001 and 0.5% by weight.

(Meth)acrylate derivatives may also be formed by the reaction ofacryloyl chloride or methacryloyl chloride with the polyester polyolsobtained in the inventive process described above, with the simultaneouselimination of hydrochloric acid, also in the presence of the abovementioned suitable free radical scavengers. (Meth)acrylate derivativesfind utility as UV-, peroxide-, oxidative-, or radiation-curableoligomers for a variety of coating applications.

Urethane (Meth)Acrylates

Urethane (meth)acrylates may also be prepared using the polyesterpolyols obtained by the inventive process described above, by reactinghydroxyethyl (meth)acrylate with an isocyanate-terminated prepolymer. Avariety of metal catalysts may be utilized to facilitate the formationof these prepolymers, including tin, bismuth, and zinc catalysts. Thereaction is typically conducted in the presence of an air or oxygenpurge at temperatures below about 140° C., and in the presence of a freeradical scavenger to avoid free radical polymerization of the(meth)acrylate functionality. Suitable free radical scavengers include,for example, phenothiazine, butylated hydroxyl toluene and1,4-hydroquinone at levels between about 0.001 and 0.5% by weight.Urethane (meth)acrylate derivatives find utility as UV-, peroxide-,oxidative-, or radiation-curable oligomers for a variety of coatingapplications.

The reaction product of an excess of polyisocyanate with the abovedescribed polyester polyols can also yield isocyanate-terminatedprepolymers. By adjusting the isocyanate to hydroxyl ratio, urethanefunctionality can also result in the prepolymer. Isocyanate terminatedprepolymers are typically viscous liquids that may subsequently beconverted to high molecular weight polyurethanes via further reactionwith water, glycols, other polyols or polyamines. The isocyanateterminated prepolymer can be reacted with hydroxyethyl methacrylate orhydroxyethyl acrylate to provide a urethane acrylate resin or a urethanemethacrylate resin.

Plasticizers Polymeric Plasticizers—Recycled PET

A recycle stream containing recycled PET and PTT containers, carpet,carpet fiber, textiles or fabric can be reacted to form a polymericplasticizer. In one embodiment, the plasticizer is produced by reacting:(a) the PET or PTT recycle stream; (b) a glycol; (c) a C₄-C₃₆monocarboxylic acid, ester or anhydride thereof; and (d) a diacid, toform a polymeric plasticizer. In another embodiment, the plasticizer canbe produced by reacting: (a) the recycle stream; (b) a glycol; (c) amono-alcohol; and (d) a diacid.

The recycle stream containing recycled PET and PTT containers, carpet,carpet fiber, textiles or fabric is as described above.

Glycols used to produce the polymeric plasticizer include ethyleneglycol, propylene glycol, 1,3-propanediol, 1,2-butanediol,1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol,1,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,3-hexanediol,1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol,2-methyl-1,3-propanediol, neopentyl glycol, glycerol,trimethylolpropane, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol,1,3-cyclohexanedimethanol, diethylene glycol, tetraethylene glycol,dipropylene glycol, triethylene glycol, tripropylene glycol,polyethylene glycol, polypropylene glycol, polycarbonate polyols,pentaerythritol, and block or random copolymer glycols of ethylene oxideand propylene oxide, aliphatic polyester polyols,2,2,4,4-tetramethyl-1,3-cyclobutanediol, and combinations thereof.

By “monocarboxylic acid”, is meant that the acid, or the ester oranhydride derived therefrom, is based on a carboxylic acid compoundhaving a single carboxylic acid group. An example of such a carboxylicacid is the C₆ monocarboxylic acid, hexanoic acid. An example of anester is the ethyl ester of hexanoic acid, which is known as ethylhexanoate. An example of an anhydride is hexanoic acid anhydride, whichis also known as hexanoic anhydride. Additionally, the anhydride can bea mixed anhydride from two different carboxylic acids, as long as one ofthe acids is from a C₄-C₃₆ monocarboxylic acid. Such an example would bethe mixed anhydride of hexanoic acid (a C₆ monocarboxylic acid, whichmeets the C₄-C₃₆ requirement) and acetic acid (a C₂ acid).

In general, the C₄-C₃₆ monocarboxylic acid, ester or anhydride thereofcan function as a chain terminator in the preparation of the polymericplasticizer compositions because when it is incorporated into thepolymerization reaction, it can cap the ends of the polymer chainstructure.

The C₄-C₃₆ monocarboxylic acid, ester or anhydride thereof can beselected from straight, branched or cyclic aliphatic compounds that canbe either saturated or unsaturated. Furthermore, aromatic compounds arealso included. Additionally, for the esters, the alcohol-derived portionis preferably derived from an alcohol having from one to seven carbonatoms, i.e. C₁ to C₇. Examples of C₄-C₃₆ monocarboxylic acid esters alsoinclude the C₁ to C₇ alcohol esters of the C₄-C₃₆ monocarboxylic acids,in other words C₄-C₃₆ monocarboxylic acids that have been esterifiedwith C₁ to C₇ alcohols. These C₁ to C₇ alcohols can include aromaticalcohols. Examples of C₄-C₃₆ monocarboxylic acid esters include alkylbenzoates, alkyl phenylacetates, alkyl esters of branched or linearsaturated or unsaturated alkyl carboxylic acids, alkyl naphthenoates,alkyl norbornene carboxylates, alkyl 2-furanoates, and combinationsthereof.

Examples of C₄-C₃₆ monocarboxylic anhydrides include anhydrides ofbenzoic acid, benzene acetic acid, branched or linear saturated orunsaturated alkyl carboxylic acids, naphthenic acid, norbornenecarboxylic acid, 2-furoic acid, and combinations thereof. Additionally,the anhydrides can include mixed anhydrides derived from two differentcarboxylic acids, such as a mixed anhydride of benzoic acid and benzeneacetic acid.

Suitable diacids that can be used to produce the polymeric plasticizersinclude succinic acid, glutaric acid, pimelic acid, suberic acid,succinic acid, pimelic acid azelaic acid, sebacic acid, adipic acid,fumaric acid, maleic acid, 1,2-cyclohexane dicarboxylic acid,1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid,2,5-furan dicarboxylic acid, 1,9-nonanedioic acid, 1,9-nonenedioic acid,1,10-decanedioic acid, 1,10-decenedioic acid, 1,11-undecanedioic acid,1,11-undecenedioic acid, 1,18-octadecanedioic acid, 1,18-octadecenedioicacid, 1,12-dodecanedioic acid, 1,12-dodecenedioic acid,1,14-tetradecanedioic acid, 1,14-tetradecenedioic acid,1,16-hexadecanedioic acid, 1,16-hexadecenedioic acid, eicosenedioicacid, eicosanedioic acid, docosanedioic acid, tetracosanedioic acid,tetracosendioic acid, and combinations thereof.

Suitable mono alcohols for the production of the polymeric plasticizerinclude C₄-C₃₆ mono alcohols. It is understood that these C₄-C₃₆alcohols are intended to be distinct from the required glycol (i.e. thediol) of the present invention. It is intended that alcohols lower thanC₄ generally are too volatile and do not have desirable characteristicsfor incorporation herein. The C₄-C₃₆ alcohol can be selected fromstraight, branched or cyclic aliphatic compounds that can be eithersaturated or unsaturated. Aromatic compounds are also intended. Also,alkoxylated alcohols are contemplated herein.

Useful C₄-C₃₆ alcohols include those selected from norborneol,alkoxylates of branched or linear alkyl phenols, branched or linearsaturated or unsaturated alkyl alcohols, alkoxylated branched or linearsaturated or unsaturated alkyl alcohols, 2-phenoxy ethanol, 2-phenoxypropanol, benzyl alcohol, furfuryl alcohol, alkoxylated furfurylalcohol, 2-(hydroxymethyl)tetrahydrofuran,6,6-dimethyl-2-norpinen-2-ethanol, and alkoxylated6,6-dimethyl-2-norpinen-2-ethanol, cyclohexanol, alkoxylatedcyclohexanol, 2-cyclohexylethanol, alkoxylated 2-cyclohexyl ethanol,2-cyclohexyloxyethanol, 1-ethynyl-1-cyclohexanol, 2-phenylethanol,alkoxylated 2-phenyl ethanol, alkoxylated phenols, alkoxylatednorborneol, farnesol, hydrogenated farnesol, geraniol, hydrogenatedgeraniol, 2-ethyl-1-hexanol, and combinations thereof.

To form the polymeric plasticizer, the recycled PET material is digestedwith the glycol in a reactor as described above. Then, the reactionmixture is cooled to 100-130° C. and the other reactants: C₄-C₃₆monocarboxylic acid, ester, anhydride, or combination thereof; diacid;or mono alcohol are added. A reaction temperature is controlled between180-250° C., and the esterification reaction is performed under nitrogensparging conditions. Any esterification by-product, for example water,and/or transesterification by-product, for example methanol or otheralcohols, is eliminated from the reaction system. The reaction isallowed to proceed until the desired acid number is achieved.

Polymeric Plasticizers—Recycled PTT

A recycle stream containing recycled polytrimethylene terephthalate(PTT) carpet can be digested and reacted as described above to form apolymeric plasticizer. In this embodiment, a stream of recycled PTTcarpet is reacted with a glycol in a reactor, thereby forming a digestedproduct stream comprising polyols, and at least one undigested stream.

After digestion of the PTT as described above, the reaction mixture iscooled to 100-130° C. and the other reactants: C₄-C₃₆ monocarboxylicacid, ester, anhydride, or combination thereof; diacid; or mono alcoholare added. A reaction temperature is controlled between 180-250° C., andthe esterification reaction is performed under nitrogen spargingconditions. Any esterification by-product, for example water, and/ortransesterification by-product, for example methanol or other alcohols,is eliminated from the reaction system. The reaction is allowed toproceed until the desired acid number is achieved.

Monomeric Plasticizers—PET & PTT carpet

PET or PTT recycle carpet fibers can be reacted with a mono alcohol toform a monomeric plasticizer. These carpet fibers can be obtained byshaving, skiving or as otherwise described above to remove the carpetbacking. Preferably, the mono alcohol is a C₄-C₃₆ mono alcohol. TheC₄-C₃₆ mono alcohol can be selected from straight, branched or cyclicaliphatic compounds that can be either saturated or unsaturated.Aromatic compounds are also included, as well as alkoxylated alcohols.Useful C₄-C₃₆ alcohols include those selected from norborneol,alkoxylates of branched or linear alkyl phenols, branched or linearsaturated or unsaturated alkyl alcohols, alkoxylated branched or linearsaturated or unsaturated alkyl alcohols, 2-phenoxy ethanol, 2-phenoxypropanol, benzyl alcohol, furfuryl alcohol, alkoxylated furfurylalcohol, 2-(hydroxymethyl)tetrahydrofuran,6,6-dimethyl-2-norpinen-2-ethanol, and alkoxylated6,6-dimethyl-2-norpinen-2-ethanol, cyclohexanol, alkoxylatedcyclohexanol, 2-cyclohexylethanol, alkoxylated 2-cyclohexyl ethanol,2-cyclohexyloxyethanol, 1-ethynyl-1-cyclohexanol, 2-phenylethanol,alkoxylated 2-phenyl ethanol, alkoxylated phenols, alkoxylatednorborneol, farnesol, hydrogenated farnesol, geraniol, hydrogenatedgeraniol, and combinations thereof.

More preferably, the mono alcohol used to prepare the monomericplasticizer is 2-ethylhexanol.

Preferably, the monomeric plasticizer product is dioctyl terephthalate.

To prepare the monomeric plasticizer, the PET or PTT carpet fibers arereacted with the mono alcohol in a reactor at 180 to 250° C., preferably185 to 200° C. for 8 to 48 hours. The resultant material is thenfiltered to remove solids. Then excess alcohol and glycol are strippedoff, e.g., via nitrogen stripping. A final filtration using a 3 to 10micron filter can be used to remove fine particles that are indigestibleand were not removed in previous filtrations.

Preferably, the plasticizers (polymeric or monomeric) prepared using thepolyols of the inventive process described above have hydroxyl values ofless than 2. The plasticizers also preferably have hydroxyl numbers of25 to 800 mg KOH/g, more preferably 35 to 500 mg KOH/g, and even morepreferably 40 to 400 mg KOH/g; acid numbers preferably, less than 30 mgKOH/g, more preferably less than 10 mg KOH/g, and most preferably lessthan 5 mg KOH/g; and preferably a viscosity of 100 to 10,000 cP, morepreferably 100 to 5,000 cP, and even more preferably 500 to 5,000 cP.

PET & PTT Preparation from Recycled PET & PTT Carpet

PET or PTT recycle carpet fibers can be reprocessed to produce new PETor PTT carpet. In this process, the shaved carpet fiber is glycolizedwith a diol to form a raw product stream containing liquid diol witholigomers of PTT or PET such as bishydroxyethyl terephthalate (BHET) andbishydroxypropyl terephthalate (BHPT). The raw product stream is thensubjected to a polycondensation reaction to form a product streamcontaining the PTT or PET. Preferably, the diols used to glycolize thecarpet files are 1,3 propane diol and ethylene glycol. PTT may be formedby simply heating the polyol resulting from the glycolysis of PTT with1,3-propanediol while removing 1,3-propanediol via distillation until ahigh molecular weight polymer is formed. PET may be formed by simplyheating the polyol resulting from the glycolysis of PET with ethyleneglycol while removing ethylene glycol via distillation until a highmolecular weight polymer is formed.

Referring to FIG. 1, shown is a flow diagram of a process for theproduction of polyester polyols and polyurethanes or polyisocyanuratesfrom recycled PET bottles. A PET bottle recycle stream 1 containingpolyolefins and various other contaminants is treated in a comminutionprocess step 100 to break up the bottles and reduce the size of thebottle fragments. The resulting comminuted stream 2 is then subjected toa metals separation process step 101 where a metals stream 3 isseparated from the de-metaled PET bottle stream 4. Both magnetic andnon-magnetic (conductive) metals can be removed in this step. Thede-metaled PET bottle stream 4 is then processed in a digestion/reactionprocess step 102 where it is digested in a glycol 13 and reacted with astream 14 containing a hydrophobe and/or a modifier to form a polyesterpolyol stream 5 containing polyolefins. An agglomeration adhesionpromoter may be optionally added during this process step to facilitateagglomeration of contaminants and polyolefins into a single phase. Thepolyester polyol stream 5 is then subjected to a liquid-solid separationprocess step 103, where a solid polyolefin stream 7 is separated fromthe liquid polyester polyol stream 6. The liquid polyester polyol stream6 is then treated in a carbon bed contacting process step 104 to removecolor bodies from the liquid polyester polyol stream 6. A decolorizedpolyester polyol stream 8 exits the carbon bed contacting process step104 and is routed to a polyurethane or polyisocyanurate production step105 where it is reacted with a polyisocyanate stream 9 to form apolyurethane, polyisocyanurate, or isocyanate-terminated prepolymerstream 10. The separated polyolefin stream 7 is routed to a polyolefinsstream processing step 106 where the polyolefins are cleaned by washingor steaming, dried and then extruded to form a polyolefin product stream12 in the form of pellets or fibers.

Referring to FIG. 2, shown is a flow diagram of a process for theproduction of polyester polyols and polyurethanes or polyisocyanuratesfrom recycled PET carpet fibers. A PET carpet recycle stream 1 a istreated in a comminution process step 200 to remove the carpet fibersfrom the carpet backing. The resulting comminuted stream 2 a is thensubjected to a metals separation process step 201 where a metals stream3 a is separated from the de-metaled PET carpet fiber stream 4 a. Bothmagnetic and non-magnetic (conductive) metals can be removed in thisstep. The de-metaled PET carpet fiber stream 4 a is then processed in adigestion/reaction process step 202 where it is digested in a glycol 13a and reacted with a stream 14 a containing a hydrophobe and/or amodifier to form a polyester polyol stream 5 a. The polyester polyolstream 5 a is then subjected to a liquid-solid separation process step203, where a filtered solids stream 7 a is separated from the liquidpolyester polyol stream 6 a. The liquid polyester polyol stream 6 a isthen treated in a carbon bed contacting process step 204 to remove colorbodies from the liquid polyester polyol stream 6 a. A decolorizedpolyester polyol stream 8 a exits the carbon bed contacting process step204 and is routed to a polyurethanes or polyisocyanurates productionstep 205 where it is reacted with a polyisocyanate stream 9 a to form apolyurethane, polyisocyanurate, or isocyanate-terminated prepolymerstream 10 a.

Referring to FIG. 3, shown is a flow diagram of a process for theproduction of polyester polyols from a recycle stream 30 of recycled PETcarpet, recycled PET bottles, recycled PET textiles and recycled PETarticles, where the recycle stream 30 is digested with glycol 31 in adigestion step 1000 to produce a stream 32 containing digested polyolsand contaminants. Optionally, emulsifiers or adhesives can be introducedinto stream 32 by stream 33. The digested polyols and contaminantsstream 32 is reacted with hydrophobes 34 and/or modifier 35 in reactionstep 1001. A polyester polyol and contaminants stream 36 exits thereaction step 1001. The polyester polyol and contaminants stream 36 canbe processed in a polyurethane, polyisocyanurates, orisocyanate-terminated prepolymer production step 1002 by reaction with apolyisocyanate stream 37 to produce a polyurethane, polyisocyanurate orisocyanate-terminated prepolymer stream 38. Alternately, the polyesterpolyols and contaminants stream 36 can be processed in liquid-solidseparation step 1003 where the liquid polyester polyol stream 40 isseparated from the solid contaminants stream 39.

Referring to FIG. 4, shown is a flow diagram of a process for theproduction of polyester polyols from a recycle stream 50 of recycled PETcarpet, recycled PET bottles, recycled PET textiles and recycled PETarticles, where the recycle stream 50 is digested with glycol 51 in adigestion step 2000 to produce a stream 52 containing digested polyolsand contaminants. Optionally, emulsifiers or adhesives can be introducedinto stream 52 by stream 53. The digested polyols and contaminantsstream 52 can be processed in a polyurethane, polyisocyanurates orisocyanate-terminated prepolymer production step 2001 by reaction with apolyisocyanate stream 54 to produce a polyurethane, polyisocyanurate orisocyanate-terminated prepolymer stream 55. Alternately, the digestedpolyols and contaminants stream 52 can be processed in a liquid-solidseparation step 2002 to produce a liquid polyol stream 57 and a solidcontaminants stream 56. The liquid polyol stream 57 is reacted withhydrophobes 58 and/or modifier 59 in reaction step 2003, to produce apolyester polyol 60.

Integrated Process

Referring to FIG. 5 shown is an integrated process for using recycledPET or PTT-based carpet to produce polyols that can be used in rigidfoams, polyisocyanurate foams, polyurethane polymers, or flexiblepolyurethane foams; monomeric plasticizers; polymeric plasticizers;recycled calcium carbonate; quick lime; slaked lime; PET; or PTT in anenvironmental-friendly and energy efficient way. The recycled PET orPTT-based carpet is treated by first separating the top surface carpetfibers from the primary carpet backing, the secondary carpet backing andthe adhesive layer used to bind the carpet structure together. Usually,the adhesive layer contains calcium carbonate as a filler, while thesecondary backing usually contains a polyolefin such as polypropylene.The primary backing may consist of a variety of polymers. The separatedfibers are treated by a step such as washing to remove dirt, mold, hairand other contaminants; filtered, dried, and then densified by extrusionto form pellets which are then fed to a glycolysis reactor. Theseparated backing is fed to an incinerator, kiln or gasifier in a powergeneration system, where the backing is combusted, optionally along withother renewable or recycle-content waste fuels such as biodiesel,municipal waste, agricultural waste or lignin. The heat of combustion isrecovered via the production of steam in a boiler, which in turn isutilized in a steam turbine to produce electricity. This electricity isthen utilized by the glycolysis reactor. Calcium exiting the combustionsystem will either be present as calcium carbonate, which can berecycled into carpet backing applications, or calcium oxide (quick lime)or calcium hydroxide (slaked lime), which can be used in industrial andagricultural applications. In one aspect of the invention, the quicklime or slaked lime is used to treat the acidic gases produced in thecombustion process.

The densified and comminuted PET or PTT carpet fibers are routed to theglycolysis reactor where they are then glycolyzed or reacted withhydrophobes, monoacids, diacids or monols, glycols, water, orcombinations thereof to produce polyols that can be used in rigid foams,polyisocyanurate foams, polyurethane polymers, or flexible polyurethanefoams; monomeric plasticizers; or polymeric plasticizers.

EXAMPLES

The following examples merely illustrate the invention; the skilledperson will recognize many variations that are within the spirit of theinvention and scope of the claims.

Hydroxyl numbers and acid numbers are determined by standard methods(ASTM E-222 and ASTM D3339, respectively).

Viscosities are measured at 25° C. using a Brookfield DV-III Ultrarheometer with spindle #31 at 25%, 50%, and 75% torque in a Thermoselaccessory for temperature control.

Color, clarity, and degree of settling are evaluated visually.

Example 1 Digestion of Recycled PET Bottles

A polyester polyol was produced using a Littleford FM130 reactorequipped with a plow mixer and high speed chopper mixer, commerciallyavailable from Littleford Day, Inc. Recycled PET bottles (12.9 kg)including caps, lids and labels were added through the top port of thereactor with the chopper operating at 3600 RPM and the reactor plowmixer at 1 RPM. During addition of the bottles, the reactor jacket wasmaintained at 230° C. After the shredding of the bottles, the reactorcontents were heated to 135° C. at a pressure of 25 inches of Hg for onehour. Vacuum was shut off and the reactor was opened to verify thatbottles had been shredded. Propylene glycol (13.72 kg), commerciallyavailable from EMCO, was charged to the reactor along with 43.5 grams oftitanium (IV) t-butoxide catalyst, commercially available from SigmaAldrich.

The reactor contents were heated from 197° C. to 200° C. and allowed toreact for 5 hours 30 minutes. The PET appeared to be fully digested withsmall, dispersed pieces of polyolefin from the caps floating at the topof the digested liquid. The reactor contents were then allowed to sitovernight.

Dimer fatty acid (11.9 kg) (Pripol™ 1017), commercially available fromCroda was then added to the reactor and the plow mixer was operated at 1RPM. The reaction was conducted at 172-175° C. at 26 inches of Hg vacuumuntil all water was removed. The OHV (hydroxyl value) for the polyol was214.6 mg KOH/g of sample with an acid value of 0.9.

Example 2 Digestion/Reaction of Recycled PET Carpet

A 2000 mL resin kettle equipped with an overhead mixer, Vigreux column,short path condenser head with distillation collection flask, heatingmantle, thermocouple, and nitrogen inlet was charged with recycledpropylene glycol (152.80 g), recycled PET polyester carpet includingpolyolefin backing, calcium carbonate filler, and latex adhesive (142.80g), and titanium (IV) butoxide (0.58 g) (˜0.1% by wt.). It was assumedthat the carpet contained 90% of PET. The mixture was heated with astirring rate of 150 RPM and nitrogen flow at 0.3 SCFH to 200° C. for 20hours. After about 5 hours, the recycled PET carpet had completelydissolved and appeared to be completely digested. The mixture was heatedovernight to ensure no particles of recycled PET carpet remained. Themixture was then cooled to about 100° C. Dimer fatty acid (190.88 g)(Croda Pripol™ 1017) was added, while the mixing rate was increased to350 rpm. When the addition was complete, the mixture was then heated to200° C., and nitrogen was increased to 1.0 SCFH. Water generated in thecondensation reaction was collected in the distillation flask untilroughly the theoretical amount was removed. When the reaction wascomplete, the reactor was allowed to cool to 100° C. and then pouredinto a jar. Undigested polyolefin backing was removed by forceps and themixture of polyol with calcium carbonate was run through a glass fritteddisc filter size ‘F’ ((4.0-5.5 μm)) at about 80° C. The resultingtransparent dark amber polyol had an OHV (hydroxyl value) of 353.0 mgKOH/g of sample and a viscosity at 25° C. of 3000 cP (centipoise).

Example 3 Digestion/Reaction of Recycled PET Textile

A 500 mL reactor equipped with an overhead mixer, Vigreux column, shortpath condenser head with distillation collection flask, heating mantle,thermocouple, and nitrogen inlet was charged with recycled propyleneglycol (97.91 g), recycled PET textile (48.50 g), and titaniumtetrabutoxide (0.30 g) (˜0.1% by wt.) and heated with stirring to 200°C. for 6.0 hr. After about 5 hours, the recycled PET textile hadcompletely dissolved and appeared to be completely digested. The mixturewas heated until no particles of recycled PET polyester textile remained(about 6 hr). When the digestion reaction was considered complete, themixture was cooled to about 100° C. Soybean oil (65.80 g) and phthalicanhydride (37.50 g) were added, while the mixing rate was increased to200 rpm. When the addition was complete, the mixture was then heated to210° C. Water generated in the condensation reaction was collected inthe distillation flask until roughly the theoretical amount was removed.When the reaction was complete, the digested intermediate was allowed tocool to 100° C. and then decanted from the reactor. Any large residualsolids were removed by filtration through cheesecloth. The resultingopaque dark purple-red polyol had an OHV (hydroxyl value) of 420.7 mgKOH/g of sample and a viscosity at 25° C. of 576 cP (centipoise). Thefinal product was then further filtered through a Buchner funnel withfilter paper to remove any residual solids that were not removed by thecheesecloth. The resulting filtered transparent dark purple-red polyolhad an OHV (hydroxyl value) of 429.9 mg KOH/g of sample and a viscosityat 25° C. of 588 cP (centipoise).

Example 4 Digestion/Reaction of PET Fibers

A 500 mL reactor equipped with an overhead mixer, Vigreux column, shortpath condenser head with distillation collection flask, heating mantle,thermocouple, and nitrogen inlet was charged with 110.83 g of apreviously prepared aromatic polyester polyol consisting of dimer fattyacid (39.3% by weight), recycled PET pellets (28.7% by weight) andrecycled propylene glycol (31.9% by weight) and 7.29 g of recycledpolyester fiber fill. The mixture was heated with stirring to 205° C.for 5.0 hr. After about 2.5 hours, the polyester fibers had completelydissolved and appeared to be completely digested. The mixture was heateduntil no particles of polyester fibers remained (about 5 hr). When thereaction was complete, the digested intermediate was allowed to cool to100° C. and then decanted from the reactor. Any residual undigestedparticulate solids were removed by filtration through cheesecloth. Theresulting opaque yellow polyol had an OHV (hydroxyl value) of 351.5 mgKOH/g of sample and a viscosity at 25° C. of 5577 cP.

Example 5 Polymeric Plasticizer from Recycled PET Bottles

A 1000 mL 4 neck round bottom flask equipped with an overhead mixer, 8inch Allihn water condenser, short path condenser head with distillationcollection flask, heating mantle, thermocouple, and nitrogen inlet wascharged with propylene glycol (166.79 g), glycerol (104.13 g), and asimulated ground (flaked) PET bottle bale stream (270.26 g). The mixturewas heated under nitrogen flow at 205° C., titanium (IV) butoxide (1.30g) (0.24% by wt.) catalyst was added when the reaction was above 110° C.After the flakes were digested by the glycols present. The mixture wasthen cooled to about 120° C. and filtered through a fritted glass discfunnel. The filtered material (350.00 g) was charged back into a 1000 mL4 neck round bottom with overhead mixing, 10 inch silver vacuum jacketedcolumn, short path condenser head with distillation collection flask,heating mantle, thermocouple, and nitrogen inlet purge. Succinic acid(167.72 g) and decanoic acid (365.01 g) were added to the reactor. Themixture was heated to 160° C. and held for 2 hours, and then heated upto 215° C. stepwise along with varied nitrogen flow rate. Theesterification reaction was completed when acid value is less than 2mgKOH/g. The reactor was allowed to cool to 100° C. and then poured intoa jar. The resulting polymeric plasticizer had an OHV (hydroxyl value)of 11.6 mg KOH/g of sample, an acid value of 1.3 mg KOH/g of sample, anda viscosity at 25° C. of 4,323 cP (centipoise).

Example 6 Polymeric Plasticizer from Recycled PET Carpet

A 2000 mL 4 neck round bottom flask equipped with an overhead mixer, 8inch Allihn water condenser, short path condenser head with distillationcollection flask, heating mantle, thermocouple, and nitrogen inlet wascharged with propylene glycol (162.86 g), glycerol (101.68 g), andshredded recycled ‘E-PET’ polyester carpet from Interface, Inc., (250.00g). The mixture was heated under nitrogen to 200° C., titanium (IV)butoxide (1.27 g) catalyst was added when the reaction was above 110° C.The reaction was held at 200° C. for 3 hours, and then temperature wasincreased to 205° C. When the recycled PET carpet dissolved and appearedto be completely digested, the mixture was then cooled to about 120° C.and filtered through a fritted glass disc funnel. The filtered material(127.36 g) was charged back into a 500 mL 4 neck round bottom withoverhead mixing, 8 inch Vigreux column, short path condenser head withdistillation collection flask, heating mantle, thermocouple, andnitrogen inlet purge. Succinic acid (112.79 g) and decanoic acid (159.24g) were added to the reactor. The mixture was then heated to 205° C.stepwise along with varied nitrogen flow rate. The esterificationreaction was finished when acidity was less than 2 mgKOH/g. The reactorwas allowed to cool to 100° C. and then poured into a jar. The resultingtransparent dark amber polyol had an OHV (hydroxyl value) of 19.0 mgKOH/g of sample, an acid value of 1.0 mg KOH/g of sample, and aviscosity at 25° C. of 1,895 cP (centipoise).

Example 7 Digestion/Reaction of Recycled Tan PET String

A 1000 mL 4 neck round bottom flask equipped with an overhead mixer,Allihn condenser column, short path condenser head with distillationcollection flask, heating mantle, thermocouple, and nitrogen inlet wascharged with recycled and cut tan colored PET string from RecycleAMP(81.19 g) and recycled propylene glycol (90.15 g). The mixture washeated with a stirring rate of 45 RPM and nitrogen flow at 0.2 SCFH to200° C. After 30 minutes, the reaction temperature was about 100° C. andtitanium (IV) butoxide catalyst (0.56 g) was added. After about 2 hours,the recycled PET string had completely dissolved into an opaque tansolution and appeared to be completely digested. The temperature wasincreased to 205° C. for about 3 hours to ensure complete PET digestion.After this, the reaction was then cooled to about 100° C. Dimer fattyacid (110.93 g) (Croda Pripol™ 1017) was added, while the mixing ratewas increased to 350 rpm. When the addition was complete, the mixturewas then heated to 200° C., and nitrogen was increased to 1.0 SCFH. TheAllihn condenser was replaced with an 8-inch Vigreux column wrapped withaluminum foil. Water generated in the condensation reaction wascollected in the distillation receiving flask. After 45 minutes thereaction temperature was increased to 205° C. for 1 hour. The acidnumber of the mixture was checked and found to be less than 2 mg KOH/g.The reactor was allowed to cool to 120° C. and then poured into ‘M’glass fritted disc filter funnel with an approximate pore size of 10 to16 microns. The material was vacuum filtered in an oven at 85° C. andthe resulting polyol was opaque tan color. The material was then mixedwith 2 wt % activated charcoal and filtered through ‘F’ glass fritteddisc filter funnel with an approximate pore size of 4.0 to 5.5 microns.The filtered polyol appeared to lose it's opacity and was now red amberand transparent. The resulting polyol had an OHV (hydroxyl value) of312.0 mg KOH/g, an acid value of 0.7 mg KOH/g, a Gardner color of 9, anda viscosity at 25° C. of 6000 cP (centipoise).

Example 8 Digestion of Densified Recycled White PET String

A 1000 mL 4 neck round bottom flask equipped with an overhead mixer,Allihn condenser column, heating mantle, thermocouple, and nitrogeninlet was charged with granules of recycled white PET string fromRecycleAMP that has been agglomerated (378.61 g) and recycled propyleneglycol (420.18 g). The mixture was heated with a stirring rate of 50 RPMand nitrogen flow at 0.2 SCFH to 200° C. After 30 minutes, the reactiontemperature was about 130° C. and titanium (IV) butoxide catalyst (1.33g) was added. After about 8 hours, the recycled PET string granules hadcompletely dissolved into an opaque white solution and appeared to befully digested. The reaction heat was turned off an allowed to cool toroom temperature overnight. The next day, the reaction heating mantlewas turned on and temperature was set to 200° C. After 3 hours theheating mantle was removed and the polyol was cooled to 120° C. Thepolyol was then poured out into a glass fritted disc filter funnel witha pore size of 10-16 microns. It was filtered in an oven at 120° C. witha vacuum pump set to 120 torr. The filtered polyol had a pale greenappearance and was transparent. The resulting polyol had an OHV(hydroxyl value) of 727.5 mg KOH/g, an acid value of 1.5 mg KOH/g, aGardner color of 2, and a viscosity at 25° C. of 710.2 cP (centipoise).

Example 9 Digestion of Densified Recycled Brown Sheared PET CarpetFibers

A 1000 mL 4 neck round bottom flask equipped with an overhead mixer,Allihn condenser column, heating mantle, thermocouple, and nitrogeninlet was charged with loose granules of densified sheared carpet fibersfrom CLEAR Landfill (211.24 g) and recycled propylene glycol (234.45 g).The mixture was heated with a stirring rate of 150 RPM and nitrogen flowat 0.3 SCFH to 200° C. After 30 minutes, the reaction temperature wasabout 170° C. and titanium (IV) butoxide catalyst (0.71 g) was added.After about 4 hours, the recycled PET carpet granules had completelydissolved into an opaque brown solution and appeared to be fullydigested. The reaction heat was turned off an allowed to cool to roomtemperature overnight. The next day, the reaction heating mantle wasturned on and temperature was set to 120° C., with mixing at 275 RPM.Approximately 2 weight percent of powdered activated charcoal was added(9.48 g) and allowed to mix with the polyol for 2 hours. The polyol wasthen poured out into a ‘F’ glass fritted disc filter funnel with a poresize of 4.5-5 microns. It was filtered in an oven at 80° C. with avacuum pump set to 130 torr. The filtered polyol had a dark brownappearance and was translucent. The resulting polyol had a hydroxylvalue of 794.6 mg KOH/g, an acid value of 2.0 mg KOH/g, a Gardner colorof greater than 18, and a viscosity at 25° C. of 653.3 cP (centipoise).

Example 10 Esterification of Example 9 with Soybean Oil

A 1000 mL 4 neck round bottom flask equipped with an overhead mixer,Vigreux column, short path distillation head with receiver flask,heating mantle, thermocouple, and nitrogen inlet was charged with theresulting polyol of Example 9 (300.00 g) and soybean oil from SigmaAldrich (485.25 g). The mixture was heated with a stirring rate of 400RPM and nitrogen flow at 1.0 SCFH to 185° C. After 1 hour and 45minutes, the reaction temperature was set to 200° C. and the nitrogenflow rate was increased to 1.3 SCFH. After another hour, the temperaturewas increased to 210° C. and allowed to react for 3 and a half morehours before the heating mantle was turned off for the day. The nextday, heat was turned on at 210° C., mixing at 375 RPM, and nitrogen 1.2SCFH. After about 2 hours, the acid number was verified to be below 2.0and the heat was shut off. The appearance of the polyol was brown andtranslucent. The resulting polyol had a hydroxyl value of 277.9 mgKOH/g, an acid value of 0.5 mg KOH/g, a Gardner color of 15, and aviscosity at 25° C. of 145.5 cP (centipoise).

Example 11 Rigid Foam Formulation with Example 10 Polyol

A 1 quart stainless steel mixing cup was charged with the resultingpolyol of Example 10 (76.48 g), a flame retardant Fyrol™ PCF (8.70 g), acatalyst Dabco® K-15 (1.73 g), another catalyst Polycat® 5 (0.14 g), asurfactant Tegostab® B8465 (2.75 g), deionized water (0.35 g), andpentane (20.07 g) as the blowing agent. The cup was mixed with a 2-inchcowles blade at 1000 RPM for 30 s before adding PAPI™ 27 polymeric MDI(148.25 g) and was then mixed at 1700 RPM for 12 s. The contents of themetal cup were poured into a paper cup in the shape of a frustum conewith the smaller diameter on the bottom surface. The foam had a creamtime of 50 seconds, a string time of 3 minutes 7 seconds, a rise time of3 minutes 31 seconds, and a final tack free time of 4 minutes. The foamwas allowed to cure overnight and the next morning the foam thatextended beyond the top of the cup was cut off. The weight of the foamin the cup was measured and the density was approximated to 2.4 poundsper cubic foot (PCF).

Example 12 Digestion of 70% Densified Recycled Brown Sheared PET CarpetFibers and 30% Polyurethane Flexible Foam

A 1000 mL 4 neck round bottom flask equipped with an overhead mixer,Allihn condenser column, heating mantle, thermocouple, and nitrogeninlet was charged with loose granules of densified sheared carpet fibersfrom CLEAR Landfill (150.64 g) and recycled propylene glycol (178.80 g).The mixture was heated with a stirring rate of 150 RPM and nitrogen flowat 0.3 SCFH to 200° C. After 45 minutes, the reaction temperature wasabout 150° C. and titanium (IV) butoxide catalyst (0.70 g) was added.After about 2 hours, the recycled PET carpet granules had completelydissolved into an opaque dark brown solution. The reaction temperaturewas set to 190° C. and allowed to cool. Next, small pieces of black andwhite polyurethane flexible foam (38.51 g) were added to the reactionover 15 minutes. After the addition, the temperature was increased to200° C. and reacted for another 5 hours. The heating mantle was removedand the polyol was cooled to 100° C. and poured into 1 L bottle. Thepolyol had a dark green-black appearance and was opaque. The resultingpolyol had an OHV (hydroxyl value) of 733.7 mg KOH/g, an acid value of2.3 mg KOH/ and a viscosity at 25° C. of 2529 cP (centipoise).

Example 13 Digestion of 50% Densified Recycled Brown Sheared PET CarpetFibers and 50% Polyurethane Flexible Foam

A 1000 mL 4 neck round bottom flask equipped with an overhead mixer,Allihn condenser column, heating mantle, thermocouple, and nitrogeninlet was charged with loose granules of densified sheared carpet fibersfrom CLEAR Landfill (150.45 g) and recycled propylene glycol (178.99 g).The mixture was heated with a stirring rate of 150 RPM and nitrogen flowat 170° C. and titanium (IV) butoxide catalyst (0.70 g) was added. Afterabout 2 hours, the recycled PET carpet granules had completely dissolvedinto an opaque dark brown solution. The reaction temperature was set to190° C. and allowed to cool. Next, small pieces of black and whitepolyurethane flexible foam (164.67 g) were added to the reaction over 1hour and 30 minutes. After the addition, the temperature was increasedto 200° C. and reacted for another 4 hours. The heating mantle wasremoved and the polyol was cooled to 100° C. and poured into 1 L bottle.The polyol had a dark green-black appearance and was opaque. Theresulting polyol had an OHV (hydroxyl value) of 553.9 mg KOH/g, an acidvalue of 1.9 mg KOH/ and a viscosity at 25° C. of 8158 cP (centipoise).

Other features, advantages and embodiments of the invention disclosedherein will be readily apparent to those exercising ordinary skill afterreading the foregoing disclosure. In this regard, while specificembodiments of the invention have been described in considerable detail,variations and modifications of these embodiments can be effectedwithout departing from the spirit and scope of the invention asdescribed and claimed.

We claim:
 1. A process comprising: (a) reacting a recycle streamselected from recycled PET carpet, PET carpet fiber, recycled PETcontainers, recycled PET textiles, other recycled PET articles, ormixtures thereof, with a glycol in a reactor, thereby forming a digestedproduct stream comprising polyols, and at least one undigested stream;and (b) reacting the digested product stream in the reactor with ahydrophobe selected from dimer fatty acids, trimer fatty acids, oleicacid, ricinoleic acid, tung oil, corn oil, canola oil, soybean oil,sunflower oil, bacterial oil, yeast oil, algae oil, castor oil,triglycerides or alkyl carboxylate esters having saturated orunsaturated C₆-C₃₆ fatty acid units, saturated or unsaturated C₆-C₃₆fatty acids, alkoxylated castor oil, saturated or unsaturated C₉-C₁₈dicarboxylic acids or diols, cardanol-based products, recycled cookingoil, branched or linear C₆-C₃₆ fatty alcohols, hydroxy-functionalmaterials derived from epoxidized, ozonized, or hydroformylated fattyesters or acids, or mixtures thereof, thereby forming a polyesterpolyol.
 2. The process of claim 1 further comprising reacting in step(b) the digested product stream with a modifier selected from C₃-C₈dicarboxylic acids, their mono or dialkyl esters, mono or dialkenylesters, or anhydrides.
 3. The process of claim 2 wherein the modifier isselected from glutaric acid, adipic acid, succinic acid, malonic acid,cyclohexane dicarboxylic acids, maleic acid, fumaric acid, itaconicacid, phthalic acid, 2,5-furandicarboxylic acid, isophthalic acid, theanhydrides thereof, or mixtures thereof.
 4. The process of claim 1wherein the recycle stream further comprises polyolefins and metalsselected from magnetically susceptible material, non-magnetic metals,induction field detectable metals, or mixtures thereof.
 5. The processof claim 4 further comprising separating the metals from the recyclestream in a metals separation step prior to step (a).
 6. The process ofclaim 1 wherein the digested stream is separated from the at least oneundigested stream in a solid-liquid separation.
 7. The process of claim6 wherein the solid-liquid separation is selected from filtration,centrifugation, decantation, flotation, flocculation and sedimentationor combinations thereof.
 8. The process of claim 1 further comprisingreacting the polyester polyol with a polyisocyanate to form apolyurethane or polyisocyanurate.
 9. The process of claim 1 wherein theundigested stream comprises undigested materials selected frompolyolefins, dyes, inorganic fillers, and other contaminants.
 10. Theprocess of claim 9 further comprising dispersing the polyolefins in thedigested stream with a mixer, thereby forming a mixture comprisingdispersed polyolefins and the polyester polyol.
 11. The process of claim10 wherein the dispersed polyolefins have a particle size range of from100 nm to 11 cm.
 12. The process of claim 10 further comprisingseparating the dispersed polyolefins from the mixture, thereby forming afiltered liquid stream comprising the polyester polyol and a polyolefinssolid stream.
 13. The process of claim 1 wherein the recycle stream hasbeen comminuted prior to step (a).
 14. A polyester polyol produced bythe process of claim
 1. 15. A process comprising: (a) reacting a recyclestream selected from recycled PET carpet, PET carpet fiber, recycled PETtextiles, bales of PET containers or mixtures thereof; with a glycol ina reactor, thereby forming a digested product stream comprising polyols,and at least one undigested stream; and (b) reacting the digestedproduct stream in the reactor with a modifier selected from C₃-C₈dicarboxylic acids, their mono or dialkyl esters, mono or dialkenylesters, or anhydrides, thereby forming a polyester polyol.
 16. Theprocess of claim 15 wherein the polyester polyol has a hydroxyl numberof 25 to 800 mg KOH/g.
 17. The process of claim 1 wherein the recycledPET containers comprise PET bottles, polyolefin caps, cap seals, labeladhesives and labels.
 18. The process of claim 1 wherein the recyclestream comprises recycled PET containers from unprocessed bottle bales.19. The process of claim 9 further comprising contacting the undigestedstream with an adhesive to promote agglomeration of undigested material.20. The process of claim 1, further comprising reacting the polyesterpolyol with acrylic acid, methacrylic acid, acryloyl chloride ormethacryloyl chloride, thereby forming an acrylate or methacrylatederivative.
 21. The process of claim 1, further comprising reacting thepolyester polyol with a polyisocyanate to form an isocyanate terminatedprepolymer.
 22. The process of claim 21 further comprising reacting theisocyanate terminated prepolymer with hydroxyethyl methacrylate orhydroxyethyl acrylate, thereby forming a urethane acrylate resin or aurethane methacrylate resin.
 23. A process comprising: (a) reacting arecycle stream selected from recycled PET carpet, PET carpet fiber,recycled PET bottles, recycled PET textiles, other recycled PETarticles, or mixtures thereof, with a glycol in a reactor, therebyforming a digested intermediate comprising polyols and contaminantsselected from colorants, dyes, pigments, inorganic fillers, undigestedpolymers or mixtures thereof; and (b) reacting the digested intermediatewith a polyisocyanate or a hydrophobe selected from dimer fatty acids,trimer fatty acids, oleic acid, ricinoleic acid, tung oil, corn oil,canola oil, soybean oil, sunflower oil, bacterial oil, yeast oil, algaeoil, castor oil, triglycerides or alkyl carboxylate esters havingsaturated or unsaturated C₆-C₃₆ fatty acid units, saturated orunsaturated C₆-C₃₆ fatty acids, alkoxylated castor oil, saturated orunsaturated C₉-C₁₈ dicarboxylic acids or diols, cardanol-based products,recycled cooking oil, branched or linear C₆-C₃₆ fatty alcohols,hydroxy-functional materials derived from epoxidized, ozonized, orhydroformylated fatty esters or acids, or mixtures thereof, therebyforming a product stream, wherein if the digested intermediate reactswith the polyisocyanate, the product stream is selected frompolyurethane, polyisocyanurate or an isocyanate terminated prepolymer,and if the digested intermediate reacts with the hydrophobe the productstream is a polyester polyol.
 24. The process of claim 23 wherein thedigested intermediate is reacted with a hydrophobe and furthercomprising reacting the polyester polyol with a modifier selected fromC₃-C₈ dicarboxylic acids, their mono or dialkyl esters, mono ordialkenyl esters, or anhydrides, thereby forming a second polyesterpolyol.
 25. The process of claim 23 wherein the contaminants areseparated from the digested intermediate in a solid-liquid separation,thereby forming a contaminant-free polyester polyol. 26.-28. (canceled)29. The process of claim 1 wherein the glycol is selected from ethyleneglycol, propylene glycol, 1,3-propanediol, 1,2-butylene glycol,1,3-butylene glycol, 1,4-butanediol, 2-methyl-1,3-propanediol,pentaerythritol, neopentyl glycol, glycerol, trimethylolpropane,2,2,4,4-tetramethyl-1,3-cyclobutanediol, 3-methyl-1,5-pentanediol,1,4-cyclohexane-dimethanol, 1,3-cyclohexanedimethanol, diethyleneglycol, dipropylene glycol, triethylene glycol, 1,6-hexanediol,tripropylene glycol, tetraethylene glycol, polyethylene glycols having anumber average molecular weight up to about 400 g/mol, block or randomcopolymers of ethylene oxide and propylene oxide, and mixtures thereof.30.-41. (canceled)
 42. The process of claim 1 wherein the polyesterpolyol is reacted with a C₄-C₃₆ monocarboxylic acid, ester or anhydride,and diacid selected from succinic acid, glutaric acid, pimelic acid,suberic acid, succinic acid, pimelic acid azelaic acid, sebacic acid,adipic acid, fumaric acid, maleic acid, 1,2-cyclohexane dicarboxylicacid, 1,3-cyclohexane dicarboxylic acid, 1,4-cyclohexane dicarboxylicacid, 2,5-furan dicarboxylic acid, 1,9-nonanedioic acid, 1,9-nonenedioicacid, 1,10-decanedioic acid, 1,10-decenedioic acid, 1,11-undecanedioicacid, 1,11-undecenedioic acid, 1,18-octadecanedioic acid,1,18-octadecenedioic acid, 1,12-dodecanedioic acid, 1,12-dodecenedioicacid, 1,14-tetradecanedioic acid, 1,14-tetradecenedioic acid,1,16-hexadecanedioic acid, 1,16-hexadecenedioic acid, eicosenedioicacid, eicosanedioic acid, docosanedioic acid, tetracosanedioic acid,tetracosendioic acid, and combinations thereof, thereby forming apolymeric plasticizer. 43.-67. (canceled)
 68. The process of claim 1,wherein the recycle stream comprises PET containers and at least one ofrecycled PET carpet and recycled PET textiles.
 69. The process of claim15 wherein the recycle stream further comprises at least one of recycledPET carpet, PTT carpet and PET textiles. 70.-81. (canceled)
 82. Theprocess of claim 25 further comprising reacting in step (b) the digestedintermediate with a modifier selected from C₃-C₈ dicarboxylic acids,their mono or dialkyl esters, mono or dialkenyl esters, diesters, oranhydrides, thereby forming a polyester polyol.
 83. (canceled) 84.(canceled)